Agricultural chemicals

ABSTRACT

The present invention relates to compounds which are of use in the field of agriculture as herbicides. The invention also relates to compositions comprising said compounds and methods of using said compounds.

The present invention relates to compounds which are of use in the fieldof agriculture as herbicides.

Given the global increase in demand for food, there is an internationalneed for new treatments to reduce food crop losses to disease, insectsand weeds. Over 40% of crops are lost before harvest, and 10% postharvest, worldwide. Losses have actually increased since the mid-1990s.

A new threat contributing to this is the emergence of chemical-resistantorganisms, for example, glyphosate-resistant weeds in USA andstrobilurin-resistant strains of septoria fungal species.

Recent research also suggests that the geographical spread of many croppests and diseases is increasing, possibly as a result of globalwarming.

An aim of the present invention is to provide pesticides (e.g.herbicides) which have activity either non-selectively, i.e. broadspectrum activity, or which are active specifically against selectivetarget organisms.

An aim of the present invention is to provide compounds which are lesspersistent in the environment after use than prior art compounds.

Alternatively or additionally the compounds of the present invention areless prone to bioaccumulation once in the food chain than prior artcompounds.

Another aim of the invention is to provide compounds which are lessharmful to humans than prior art compounds.

Alternatively or additionally, the compounds of the invention may beless harmful than prior art compounds to one or more of the followinggroups: amphibians, fish, mammals (including domesticated animals suchas dogs, cats, cows, sheep, pigs, goats, etc), reptiles, birds, andbeneficial invertebrates (e.g. bees and other insects, or worms),beneficial nematodes, beneficial fungi and nitrogen-fixing bacteria.

The compounds of the invention may be as active or more active thanprior art compounds. They may have activity against organisms which havedeveloped a resistance to prior art compounds. However, the presentinvention also concerns compounds which have a lower level of activityrelative to that of prior art compounds. These lower activity compoundsare still effective as herbicides but have other advantages relative toexisting compounds such as, for example, a reduced environmental impact.

The compounds of the invention may be more selective than the parent,i.e. they may have better, similar or even slightly lower activity thanprior art compounds against target species but have a significantlylower activity against non-target species (e.g. the crops which arebeing protected).

This invention provides compounds that achieve one or more of the aboveaims. The compounds may be active in their own right or may metaboliseor react in aqueous media to yield an active compound.

SUMMARY OF THE INVENTION

Pyrimidones

In a first aspect of the invention is provided a compound of formula I:

wherein

represents a single bond or a double bond;

X is independently NR⁶ or CR⁷R⁷;

X¹ is selected from: ═O. —R⁷ or (—R⁷)₂; with the proviso that if X¹ is═O, X is CR⁷R⁷;

R¹ and R³ are each independently at each occurrence selected from C₁-C₄alkyl, C₁-C₄-haloalkyl, halogen, nitro, OR⁸, SR⁸, cyano, C₂-C₄ alkenyl,C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR⁸R⁸;

R² and R⁶ are each independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

R⁴ is absent or is independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

R⁵ is independently selected from C₁-C₄ alkyl, C₃-C₆-cycloalkyl andC₁-C₄ haloalkyl;

R⁷ is independently at each occurrence selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

R⁸ is independently at each occurrence selected from; H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl;

n is an integer selected from 0, 1 and 2;

p is an integer independently selected from 0, 1, 2 and 3;

wherein in any R¹-R⁸ group which contains an alkyl, haloalkyl,cycloalkyl, heterocycloalkyl, aryl (including phenyl, biphenyl andnaphthyl) or heteroaryl group, that alkyl, haloalkyl, cycloalkyl,heterocycloalkyl, aryl or heteroaryl group is optionally substituted,where chemically possible, by 1 to 4 substituents which are eachindependently selected at each occurrence from the group consisting of:oxo; ═NR^(a); ═NOR^(a); R^(a); halo; nitro; cyano; NR^(a)R^(a);SO₃R^(a); SO₂R^(a); SO₂NR^(a)R^(a); CO₂R^(a); C(O)R^(a); CONR^(a)R^(a);CH₂NR^(a)R^(a); CH₂OR^(a) and OR^(a);

wherein R^(a) is selected from H, C₁-C₄ alkyl and C₁-C₄ haloalkyl; andwherein, in the case of an aryl group or heteroaryl group, any two ofthese substituents (e.g. NR^(a)R^(a), OR^(a), SR^(a), R^(a)) whenpresent on neighbouring atoms in the aryl or heteroaryl group may, wherechemically possible, together with the atoms to which they are attachedform a ring which is fused to the aryl or heteroaryl group;

or an agronomically acceptable salt or N-oxide thereof.

For the absence of doubt, to satisfy valency requirements, when

is a double bond, R⁴ is absent. Thus,

may represent a single bond or be absent. Likewise, when

represents a double bond,

X¹ is —R⁷ and when

is a single bond,

X¹ is selected from ═O and (—R⁷)₂.

The compound may be a compound of formula Ia:

wherein

represents a single bond or a double bond;

X is independently NR⁶ or CR⁷R⁷;

R¹ and R³ are each independently at each occurrence selected from C₁-C₄alkyl, C₁-C₄-haloalkyl, halogen, nitro, OR⁸, SR⁸, cyano, C₂-C₄ alkenyl,C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR⁸R⁸;

R² and R⁶ are each independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

R⁴ is absent or is independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

R⁵ is independently selected from C₁-C₄ alkyl, C₃-C₆-cycloalkyl andC₁-C₄ haloalkyl;

R⁷ is independently at each occurrence selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

R⁸ is independently at each occurrence selected from; H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl;

n is an integer selected from 0, 1 and 2;

p is an integer independently selected from 0, 1, 2 and 3;

wherein in any R¹-R⁸ group which contains an alkyl, haloalkyl,cycloalkyl, heterocycloalkyl, aryl (including phenyl, biphenyl andnaphthyl) or heteroaryl group, that alkyl, haloalkyl, cycloalkyl,heterocycloalkyl, aryl or heteroaryl group is optionally substituted,where chemically possible, by 1 to 4 substituents which are eachindependently selected at each occurrence from the group consisting of:oxo; ═NR^(a); ═NOR^(a); R^(a); halo; nitro; cyano; NR^(a)R^(a);SO₃R^(a); SO₂R^(a); SO₂NR^(a)R^(a); CO₂R^(a); C(O)R^(a); CONR^(a)R^(a);CH₂NR^(a)R^(a); CH₂OR^(a) and OR^(a);

wherein R^(a) is selected from H, C₁-C₄ alkyl and C₁-C₄ haloalkyl; andwherein, in the case of an aryl group or heteroaryl group, any two ofthese substituents (e.g. NR^(a)R^(a), OR^(a), SR^(a), R^(a)) whenpresent on neighbouring atoms in the aryl or heteroaryl group may, wherechemically possible, together with the atoms to which they are attachedform a ring which is fused to the aryl or heteroaryl group;

or an agronomically acceptable salt or N-oxide thereof.

In an embodiment, the compound of formula I or formula Ia is a compoundof formula II:

wherein R¹, R², R³, R⁵, X, n and p are as described above for compoundsof formula I or formula Ia.

In an embodiment, the compound of formula I or formula Ia is a compoundof formula III:

wherein R¹, R², R³, R⁵, X, n and p are as described above for compoundsof formula I or formula Ia and wherein R⁴ is independently selectedfrom: H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.

In an embodiment, the compound of formula I or formula Ia is a compoundof formula IV:

wherein

, R¹, R², R³, R⁴, R⁵, R⁷, n and p are as described above for compoundsof formula I or formula Ia.

In an embodiment, the compound of formula I or formula Ia is a compoundof formula V:

wherein R¹, R², R³, R⁵, R⁶, n and p are as described above for compoundsof formula I or formula Ia.

In an embodiment, the compound of formula I or formula Ia is a compoundof formula VI:

wherein R¹, R², R³, R⁵, R⁶, n and p are as described above for compoundsof formula I or formula Ia and wherein R⁴ is independently selectedfrom: H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.

In an embodiment, the compound of formula I or formula Ia is a compoundof formula VII:

wherein R¹, R², R³, R⁵, R⁷, n and p are as described above for compoundsof formula I or formula Ia and wherein R⁴ is independently selectedfrom: H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.

In an embodiment, the compound of formula I is a compound of formulaXXIX:

wherein R¹, R², R³, R⁵, R⁷, n and p are as described above for compoundsof formula I and wherein R⁴ is independently selected from: H, C₁-C₄alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.

The following embodiments apply to compounds of any of formulae(I)-(VIII) and (XXIX) (including formula Ia). These embodiments areindependent and interchangeable. Any one embodiment may be combined withany other embodiment, where chemically allowed. In other words, any ofthe features described in the following embodiments may (wherechemically allowable) be combined with the features described in one ormore other embodiments. In particular, where a compound is exemplifiedor illustrated in this specification, any two or more of the embodimentslisted below, expressed at any level of generality, which encompass thatcompound may be combined to provide a further embodiment which formspart of the present disclosure.

In an embodiment,

represents a single bond. In another embodiment,

represents a double bond.

In an embodiment, X is NR⁶. Preferably R⁶ is C₁-C₄ alkyl, e.g. methyl.Thus, X may be NMe.

In another embodiment, X is CR⁷R⁷. It may be that R⁷ is at oneoccurrence H. It may be that R⁷ is at one occurrence independentlyselected from C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl. Thus,it may be that R⁷ is at one occurrence H and at the other occurrenceindependently selected from C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄haloalkyl. Preferably, R⁷ is at one occurrence H and at the otheroccurrence C₁-C₄ alkyl, e.g. methyl. Thus, X may be CHMe.

X¹ may be ═O.

X¹ may be —R⁷, e.g. H.

X¹ may be (—R⁷)₂, e.g. (—H)₂.

In an embodiment, n is 1. In another embodiment, R¹ is independentlyselected from: C₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen and C₃-C₆cycloalkyl. Thus, R¹ may be C₁-C₄-haloalkyl, e.g. CF₃.

In an embodiment, R³ is independently selected from: C₁-C₄ alkyl,C₁-C₄-haloalkyl, halogen and C₃-C₆ cycloalkyl. It may be that R³ is ateach occurrence halogen. Said halogen substituents may be the same ordifferent. If, for example, p is 2, R³ may be at both occurrences F. Asanother example, if p is 2, R³ may be at one occurrence Cl and at theother occurrence F.

In an embodiment, R² is independently selected from: C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl. Thus, R² may be C₁-C₄ alkyl.Preferably, R² is methyl.

R⁴ is present when

represents a single bond and absent when

represents a double bond. When present, R⁴ is preferably H.

In an embodiment, R⁵ is C₁-C₄ alkyl, e.g. propyl (i.e. n-propyl orisopropyl). Most preferably, R⁵ is isopropyl.

1,2-Diphenyl Ethyl Compounds

In a second aspect of the invention is provided a compound of formulaVIII:

wherein Y is independently selected from O, NR¹³ and CR¹⁴R¹⁴;

R⁹ and R¹² are each independently at each occurrence selected from C₁-C₄alkyl, C₁-C₄-haloalkyl, halogen, nitro, OR¹⁵, SR¹⁵, cyano, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR¹⁵R¹⁵;

R^(10a) is independently selected from CN and —C≡C—R^(10c);

R^(10b) is independently selected from: H, C₁-C₄ alkyl and C₁-C₄haloalkyl;

R^(10c) is independently selected from H and C₁-C₂-alkyl;

R¹¹ is selected from H, OR^(16a), C(O)R^(16a), CO₂—R^(16b),CH₂—O—R^(16b), S(O)OR^(16b), SO₃R^(16b) and P(O)(OR^(16b))₂; with theproviso that if Y is CR¹⁴R¹⁴ and R¹⁰ is CN, R¹¹ is not CO₂R^(16b);

R¹³, R¹⁴ and R^(16b) are each independently at each occurrence selectedfrom: H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

R^(16a) is independently selected from: unsubstituted C₁-C₄ alkyl,C₃-C₆-cycloalkyl and unsubstituted C₁-C₄ haloalkyl;

R¹⁵ is independently at each occurrence selected from; H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl;

q and r are each independently an integer selected from 0, 1, 2, 3, 4and 5;

wherein in any R⁹-R¹⁵, R^(16a) or R^(16b) group which contains an alkyl,haloalkyl, cycloalkyl, heterocycloalkyl, aryl (including phenyl,biphenyl and naphthyl) or heteroaryl group, that alkyl, haloalkyl,cycloalkyl, heterocycloalkyl, aryl or heteroaryl group is optionallysubstituted, where chemically possible, by 1 to 4 substituents which areeach independently selected at each occurrence from the group consistingof: oxo; ═NR^(a); ═NOR^(a); R^(a); halo; nitro; cyano; NR^(a)R^(a);SO₃R^(a); SO₂R^(a); SO₂NR^(a)R^(a); CO₂R^(a), C(O)R^(a); CONR^(a)R^(a);CH₂NR^(a)R^(a); CH₂OR^(a) and OR^(a);

wherein R^(a) is selected from H, C₁-C₄ alkyl and C₁-C₄ haloalkyl; andwherein, in the case of an aryl group or heteroaryl group, any two ofthese substituents (e.g. NR^(a)R^(a), OR^(a), SR^(a), R^(a)) whenpresent on neighbouring atoms in the aryl or heteroaryl group may, wherechemically possible, together with the atoms to which they are attachedform a ring which is fused to the aryl or heteroaryl group;

or an agronomically acceptable salt or N-oxide thereof,

with the proviso that the compound is not

The compound may be a compound of formula VIIIa:

wherein Y is independently selected from O, NR¹³ and CR¹⁴R¹⁴;

R⁹ and R¹² are each independently at each occurrence selected from C₁-C₄alkyl, C₁-C₄-haloalkyl, halogen, nitro, OR¹⁵, SR¹⁵, cyano, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR¹⁵R¹⁵;

R¹⁰ is independently selected from CN and C₂-C₄-alkynyl;

R¹¹ is independently selected from C(O)R¹⁶, CO₂—R¹⁶, CH₂—O—R¹⁶,S(O)OR¹⁶, SO₃R¹⁶ and P(O)(OR¹⁶)₂; with the proviso that if Y is CR¹⁴R¹⁴and R¹⁰ is CN, R¹¹ is not CO₂R¹⁶;

R¹³, R¹⁴ and R¹⁶ are each independently at each occurrence selectedfrom: H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

R¹⁵ is independently at each occurrence selected from; H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl;

q and r are each independently an integer selected from 0, 1, 2, 3, 4and 5;

wherein in any R⁹-R¹⁶ group which contains an alkyl, haloalkyl,cycloalkyl, heterocycloalkyl, aryl (including phenyl, biphenyl andnaphthyl) or heteroaryl group, that alkyl, haloalkyl, cycloalkyl,heterocycloalkyl, aryl or heteroaryl group is optionally substituted,where chemically possible, by 1 to 4 substituents which are eachindependently selected at each occurrence from the group consisting of:oxo; ═NR^(a); ═NOR^(a); R^(a); halo; nitro; cyano; NR^(a)R^(a);SO₃R^(a); SO₂R^(a); SO₂NR^(a)R^(a); CO₂R^(a); C(O)R^(a); CONR^(a)R^(a);CH₂NR^(a)R^(a); CH₂OR^(a) and OR^(a);

wherein R^(a) is selected from H, C₁-C₄ alkyl and C₁-C₄ haloalkyl; andwherein, in the case of an aryl group or heteroaryl group, any two ofthese substituents (e.g. NR^(a)R^(a), OR^(a), SR^(a), R^(a)) whenpresent on neighbouring atoms in the aryl or heteroaryl group may, wherechemically possible, together with the atoms to which they are attachedform a ring which is fused to the aryl or heteroaryl group;

or an agronomically acceptable salt or N-oxide thereof.

In an embodiment, the compound of formula VIII or formula VIIIa is acompound of formula IX:

wherein R⁹, R¹², R^(16a), q and r are as described above for compoundsof formula VIII or formula VIIIa.

In an embodiment, the compound of formula VIII is a compound of formulaX:

wherein R⁹, R¹², R^(16b), q and r are as described above for compoundsof formula VIII.

In an embodiment, the compound of formula VIIIa is a compound of formulaXa:

wherein R⁹, R¹², R¹⁶, q and r are as described above for compounds offormula VIIIa.

In an embodiment, the compound of formula VIII or formula VIIIa is acompound of formula XI:

wherein R⁹, R¹², R^(16a), q and r are as described above for compoundsof formula VIII or formula VIIIa.

In an embodiment, the compound of formula VIII or formula VIIIa is acompound of formula XII:

wherein R⁹, R¹², R¹³, R^(16a), q and r are as described above forcompounds of formula VIII or formula VIIIa.

In an embodiment, the compound of formula VIII or formula VIIIa is acompound of formula XIII:

wherein R⁹, R¹², R¹³, R^(16b), q and r are as described above forcompounds of formula VIII or formula VIIIa.

In an embodiment, the compound of formula VIII or formula VIIIa is acompound of formula XIV:

wherein R⁹, R¹², R¹³, R^(16b), q and r are as described above forcompounds of formula VIII or formula VIIIa.

In an embodiment, the compound of formula VIII or formula VIIIa is acompound of formula XV:

wherein R⁹, R¹², R^(16a), q and r are as described above for compoundsof formula VIII or formula VIIIa.

In an embodiment, the compound of formula VIII or formula VIIIa is acompound of formula XVI:

wherein R⁹, R¹², R^(16a), q and r are as described above for compoundsof formula VIII or formula VIIIa.

In an embodiment, the compound of formula VIII or formula VIIIa is acompound of formula XVII:

wherein R⁹, R¹², R^(16a), q and r are as described above for compoundsof formula VIII or formula VIIIa.

The following embodiments apply to compounds of any of formulae(VIII)-(XVII) (including formulae VIIIa and Xa). These embodiments areindependent and interchangeable. Any one embodiment may be combined withany other embodiment, where chemically allowed. In other words, any ofthe features described in the following embodiments may (wherechemically allowable) be combined with the features described in one ormore other embodiments. In particular, where a compound is exemplifiedor illustrated in this specification, any two or more of the embodimentslisted below, expressed at any level of generality, which encompass thatcompound may be combined to provide a further embodiment which formspart of the present disclosure.

In an embodiment, q is 1. Where q is 1 it may be that the single R⁹ isat the 4-position on the phenyl ring (with the rest of the moleculebeing at the 1 position). In an embodiment, R⁹ is selected from isindependently selected from: C₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen andC₃-C₆ cycloalkyl. In an embodiment, R⁹ is halogen, e.g. fluoro. Thus, R⁹may be a halogen (e.g. fluoro) at the 4-position on the phenyl ring(with the rest of the molecule being at the 1 position).

In an embodiment, r is 4. In an embodiment, R¹² is independentlyselected from: C₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen and C₃-C₆cycloalkyl. It may be that R¹² is at each occurrence halogen. Saidhalogen substituents may be the same or different. If, for example, r is2 or 4, R¹² may be at all occurrences F. As another example, if r is 4,R³ may be at one occurrence Cl and at the other three occurrences F. Ina specific embodiment, the phenyl ring to which the R¹² groups areattached is

In another specific embodiment, the phenyl ring to which the R¹² groupsare attached is

In an embodiment, R¹⁰ is CN. In an alternative embodiment, R¹⁰ isC₂-C₄-alkynyl, e.g. ethynyl.

In an embodiment, R^(10a) is CN. In an alternative embodiment, R^(10a)is —C≡C—R^(10a). Preferably, R^(10a) is ethynyl (i.e. —C≡C—H).

R^(10b) is independently selected from: H, C₁-C₄ alkyl and C₁-C₄haloalkyl. R^(10b) may be selected from H, Me and CF₃. R^(10b) may beMe. Preferably, R^(10b) is H.

In an embodiment, Y is O. Preferably, however, Y is not O. Thus, Y maybe selected from NR¹³ and CR¹⁴R¹⁴.

In another embodiment, Y is NR¹³. R¹³ is preferably H. Thus Y may be NH.In yet another embodiment, Y is CR¹⁴R¹⁴. R¹⁴ is preferably at eachoccurrence H. Thus, Y may be CH₂.

R¹¹ may be selected from C(O)R^(16a), CO₂—R^(16b), CH₂—O—R^(16b),S(O)OR^(16b), SO₃R^(16b) and P(O)(OR^(16b))₂.

In an embodiment, R¹¹ is C(O)R¹⁶. In an alternative embodiment. R¹¹ maybe CH₂—O—R¹⁶. In these embodiments, R¹⁶ is preferably C₁-C₄ alkyl, e.g.methyl.

In further embodiments, R¹¹ is S(O)OR¹⁶ or R¹¹ is SO₃R¹⁶ or R¹¹ isP(O)(OR¹⁶)₂. In these embodiments, R¹⁶ is preferably H.

Alternatively, R¹¹ may be CO₂—R¹⁶. In this embodiment, R¹⁶ may beindependently selected from H or C₁-C₄ alkyl. Thus, R¹¹ may be CO₂H orR¹¹ may be CO₂Me.

Furazans, tetrazoles and 1,2,4-triazoles

In a third aspect of the invention is provided a compound of formulaXVIII:

wherein A is independently selected from a furazan, a tetrazole and a1,2,4-triazole L is independently selected from: —NR¹⁹—CH₂—, —O—N═CH—,—N═CH— and —NR¹⁹SO₂—;

R¹⁸ is independently at each occurrence selected from C₁-C₄ alkyl,C₁-C₄-haloalkyl, halogen, nitro, OR²⁰, SR²⁰, SO₂R²⁰, cyano, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR²⁰R²⁰;

R¹⁹ is independently selected from H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl andC₁-C₄ haloalkyl;

R²⁰ is independently at each occurrence selected from H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl;

s is an integer independently selected from 0, 1, 2, 3, 4 and 5;

wherein in any R¹⁷-R²⁰ group which contains an alkyl, haloalkyl,cycloalkyl, heterocycloalkyl, aryl (including phenyl, biphenyl andnaphthyl) or heteroaryl group, that alkyl, haloalkyl, cycloalkyl,heterocycloalkyl, aryl or heteroaryl group is optionally substituted,where chemically possible, by 1 to 4 substituents which are eachindependently selected at each occurrence from the group consisting of:oxo; ═NR^(a); ═NOR^(a); R^(a); halo; nitro; cyano; NR^(a)R^(a);SO₃R^(a); SO₂R^(a); SO₂NR^(a)R^(a); CO₂R^(a); C(O)R^(a); CONR^(a)R^(a);CH₂NR^(a)R^(a); CH₂OR^(a) and OR^(a);

wherein R^(a) is selected from H, C₁-C₄ alkyl and C₁-C₄ haloalkyl; andwherein, in the case of an aryl group or heteroaryl group, any two ofthese substituents (e.g. NR^(a)R^(a), OR^(a), SR^(a), R^(a)) whenpresent on neighbouring atoms in the aryl or heteroaryl group may, wherechemically possible, together with the atoms to which they are attachedform a ring which is fused to the aryl or heteroaryl group;

or an agronomically acceptable salt or N-oxide thereof.

Where L is described as —NR¹⁹—CH₂—, it is intended that the nitrogenatom of the NR¹⁹ portion of L is directly bonded to A and the carbonatom of the CH₂ portion of L is directly bonded to the phenyl ring ofthe compounds of the invention. Likewise, where L is described as—O—N═CH—, it is intended that the oxygen atom of the —O—N portion of Lis directly bonded to A and the carbon atom of the CH portion of L isdirectly bonded to the phenyl ring of the compounds of the invention.Likewise, where L is described as —N═CH—, it is intended that thenitrogen atom of L is directly bonded to A and the carbon atom of the CHportion of L is directly bonded to the phenyl ring of the compounds ofthe invention. Likewise, where L is described as —NR¹⁹SO₂—, it isintended that the nitrogen atom of the NR¹⁹ portion of L is directlybonded to A and the sulfur atom of the S(O)₂ portion of L is directlybonded to the phenyl ring of the compounds of the invention.

In an embodiment, the compound of formula XVIII is a compound of formulaXIX:

wherein L, R¹⁸ and s are as described above for compounds of formulaXVIII and wherein R¹⁷ is independently at each occurrence selected fromC₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen, nitro, OR²⁰, SR²⁰, SO₂R²⁰, cyano,C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR²⁰R²⁰.

In an embodiment, the compound of formula XVIII is a compound of formulaXX:

wherein L, R¹⁸ and s are as described above for compounds of formulaXVIII and wherein Z is independently selected from N and CR¹⁷; R¹⁷ isindependently at each occurrence selected from C₁-C₄ alkyl,C₁-C₄-haloalkyl, halogen, nitro, OR²⁰, SR²⁰, SO₂R²⁰, cyano, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR²⁰R²⁰; and R²¹ isindependently selected from H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄haloalkyl.

Bicyclic Heteroaryl Compounds

In a fourth aspect of the invention is provided a compound of formulaXXI:

wherein

R²² is independently selected from

Z¹ and Z² are each independently selected from N and CR¹⁷;

R¹⁷ and R¹⁸ are each independently at each occurrence selected fromC₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen, nitro, OR²⁰, SR²⁰, SO₂R²⁰, cyano,C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR²⁰R²⁰;

R²⁰ is independently at each occurrence selected from H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl;

R²¹ is independently at each occurrence selected from H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl;

s is an integer independently selected from 0, 1, 2, 3, 4 and 5;

wherein in any R¹⁷-R²¹ group which contains an alkyl, haloalkyl,cycloalkyl, heterocycloalkyl, aryl (including phenyl, biphenyl andnaphthyl) or heteroaryl group, that alkyl, haloalkyl, cycloalkyl,heterocycloalkyl, aryl or heteroaryl group is optionally substituted,where chemically possible, by 1 to 4 substituents which are eachindependently selected at each occurrence from the group consisting of:oxo; ═NR^(a); ═NOR^(a); R^(a); halo; nitro; cyano; NR^(a)R^(a);SO₃R^(a); SO₂R^(a); SO₂NR^(a)R^(a); CO₂R^(a); C(O)R^(a); CONR^(a)R^(a);CH₂NR^(a)R^(a); CH₂OR^(a) and OR^(a);

wherein R^(a) is selected from H, C₁-C₄ alkyl and C₁-C₄ haloalkyl; andwherein, in the case of an aryl group or heteroaryl group, any two ofthese substituents (e.g. NR^(a)R^(a), OR^(a), SR^(a), R^(a)) whenpresent on neighbouring atoms in the aryl or heteroaryl group may, wherechemically possible, together with the atoms to which they are attachedform a ring which is fused to the aryl or heteroaryl group;

or an agronomically acceptable salt or N-oxide thereof.

The compounds described in the third and fourth aspects of the inventionare related. Thus, where designations (e.g. R¹⁸) are shared across bothaspects, the groups those designations represent have the samedefinitions.

In an embodiment, the compound of formula XVIII is a compound of formulaXXII:

wherein R¹⁸, R¹⁹ and s are as described above for compounds of formulaXVIII and wherein R¹⁷ is as described above for compounds of formulaXIX.

In an embodiment, the compound of formula XVIII is a compound of formulaXXIII:

wherein R¹⁸, R¹⁹ and s are as described above for compounds of formulaXVIII and wherein R¹⁷ is as described above for compounds of formulaXIX.

In an embodiment, the compound of formula XVIII is a compound of formulaXXIV:

wherein R¹⁸ and s are as described above for compounds of formula XVIIIand wherein R¹⁷ is as described above for compounds of formula XIX.

In an embodiment, the compound of formula XXII is a compound of formulaXXV:

wherein R¹⁸, and s are as described above for compounds of formula XXIIand wherein Z and R²¹ are as described above for compounds of formulaXX.

In an embodiment, the compound of formula XXII is a compound of formulaXXVI:

wherein R¹⁸ and s are as described above for compounds of formula XXIIand wherein Z and R²¹ are as described above for compounds of formulaXX.

In an embodiment, the compound of formula XXI is a compound of formulaXXVII:

wherein Z¹, Z², R¹⁷, R¹⁸, R²¹ and s are as described above for compoundsof formula XXI.

In an embodiment, the compound of formula XXI is a compound of formulaXXVIII:

The following embodiments apply to compounds of any of formulae(XVIII)-(XXVIII). These embodiments are independent and interchangeable.Any one embodiment may be combined with any other embodiment, wherechemically allowed. In other words, any of the features described in thefollowing embodiments may (where chemically allowable) be combined withthe features described in one or more other embodiments. In particular,where a compound is exemplified or illustrated in this specification,any two or more of the embodiments listed below, expressed at any levelof generality, which encompass that compound may be combined to providea further embodiment which forms part of the present disclosure.

In an embodiment, R¹⁷ is independently selected from: H, C₁-C₄ alkyl,C₁-C₄-haloalkyl, halogen and C₃-C₆ cycloalkyl. Thus, R¹⁷ may beindependently selected from C₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen andC₃-C₆ cycloalkyl. In a specific embodiment, R¹⁷ is C₁-C₄ alkyl;preferably, R¹⁷ is methyl. In another specific embodiment, R¹⁷ is ateach occurrence H.

In an embodiment, R¹⁸ is independently at each occurrence selected from:C₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen, SO₂R²⁰ and C₃-C₆ cycloalkyl. Itmay be that at one occurrence R¹⁸ is C₁-C₄ alkyl, e.g. methyl. It may bethat at one or more occurrences R¹⁸ is SO₂R²⁰, e.g. SO₂Me. It may bethat at one occurrence R¹⁸ is C₁-C₄ haloalkyl, e.g. CF₃. It may also bethat at one occurrence R¹⁸ is halo. In an embodiment, s is 3. In aspecific embodiment, s is 3 and R¹⁸ represents respectively, a C₁-C₄alkyl (e.g. methyl) group, a SO₂R²⁰ (e.g. SO₂Me) group and a C₁-C₄haloalkyl (e.g. CF₃) group. Alternatively, s is 3 and R¹⁸ represents atone occurrence a C₁-C₄ alkyl (e.g. methyl) group and at the other twooccurrences a SO₂R²⁰ (e.g. SO₂Me) group. In another embodiment, s is 2.In a specific embodiment, s is 2 and R¹⁸ represents respectively ahalogen (e.g. Cl) group and a SO₂R²⁰ (e.g. SO₂Me).

In a specific embodiment, the phenyl ring to which the R¹⁸ groups areattached is

In another specific embodiment, the phenyl ring to which the R¹⁸ groupsare attached is

In yet another specific embodiment, the phenyl ring to which the R¹⁸groups are attached is

In an embodiment, L is —NR¹⁹—CH₂—. Preferably, R¹⁹ is H. Thus, L may be—NHCH₂—. Alternatively, L may be —O—N═CH—. In another alternative, L maybe —N═CH—. In yet another alternative embodiment, L is —NR¹⁹SO₂—. Thus,L may be NHSO₂.

In an embodiment, Z¹ is CR¹⁷, e.g. CH. Alternatively, Z¹ is N.

In an embodiment, Z² is CR¹⁷, e.g. CH. Preferably, Z² is N.

In an embodiment, R²¹ is H. In another embodiment, R²¹ is C₁-C₄ alkyl,e.g. methyl.

In an embodiment, Z is CR¹⁷, e.g. CH. Preferably, Z is N. In a preferredembodiment, the heterocyclic portion of compounds of formulae XX, XXVand XXVI is

In an embodiment, Z¹ is CR¹⁷, e.g. CH. Alternatively, Z¹ is N.

In an embodiment, Z² is CR¹⁷, e.g. CH. Alternatively, Z² is N.

In an embodiment R²² is

In another embodiment, R²² is

In yet another embodiment, R²² is

In an embodiment, R²² is

In another embodiment, R²² is

In any of the above aspects and embodiments, heteroaryl groups may beany aromatic (i.e. a ring system containing 2(2n+1)π electrons) 5-10membered ring system comprising from 1 to 4 heteroatoms independentlyselected from O, S and N (in other words from 1 to 4 of the atomsforming the ring system are selected from O, S and N). Thus, anyheteroaryl groups may be independently selected from: 5 memberedheteroaryl groups in which the heteroaromatic ring is substituted with1-4 heteroatoms independently selected from O, S and N; and 6-memberedheteroaryl groups in which the heteroaromatic ring is substituted with1-3 (e.g. 1-2) nitrogen atoms; 9-membered bicyclic heteroaryl groups inwhich the heteroaromatic system is substituted with 1-4 heteroatomsindependently selected from O, S and N; 10-membered bicyclic heteroarylgroups in which the heteroaromatic system is substituted with 1-4nitrogen atoms. Specifically, heteroaryl groups may be independentlyselected from: pyrrole, furan, thiophene, pyrazole, imidazole, oxazole,isoxazole, triazole, oxadiazole, thiadiazole, tetrazole; pyridine,pyridazine, pyrimidine, pyrazine, triazine, indole, isoindole,benzofuran, isobenzofuran, benzothiophene, indazole, benzimidazole,benzoxazole, benzthiazole, benzisoxazole, purine, quinoline,isoquinoline, cinnoline, quinazoline, quinoxaline, pteridine,phthalazine, naphthyridine. Heteroaryl groups may also be 6-memberedheteroaryl groups in which the heteroaromatic ring is substituted with 1heteroatomic group independently selected from 0, S and NH and the ringalso comprises a carbonyl group. Such groups include pyridones andpyranones.

In any of the above aspects and embodiments, a heterocycloalkyl group isa 3-8 membered saturated or partially ring comprising 1 or 2 heteroatomsindependently selected from 0, S and N (in other words from 1 to 2 ofthe atoms forming the ring system are selected from 0, S and N). Bypartially saturated it is meant that the ring may comprise one or twodouble bonds. This applies particularly to rings with from 5 to 8members. The double bond will typically be between two carbon atoms butmay be between a carbon atom and a nitrogen atom. Examples ofheterocycloalkyl groups include; piperidine, piperazine, morpholine,thiomorpholine, pyrrolidine, tetrahydrofuran, tetrahydrothiophene,dihydrofuran, tetrahydropyran, dihydropyran, dioxane, azepine.

In any of the above aspects and embodiments, a haloalkyl group may haveany amount of halogen substituents. The group may contain a singlehalogen substituent, it may have two or three halogen substituents, orit may be saturated with halogen substituents.

In an embodiment, in any R¹-R²² group which contains an aryl orheteroaryl group, that aryl or heteroaryl group is optionallysubstituted, where chemically possible, by 1 to 4 substituents which areeach independently selected at each occurrence from the group consistingof: R^(a); halo; nitro; cyano; NR^(a)R^(a); SO₃R^(a); SO₂R^(a);SO₂NR^(a)R^(a); CO₂R^(a); C(O)R^(a); CONR^(a)R^(a); CH₂NR^(a)R^(a);CH₂OR^(a); and OR^(a); wherein R^(a) is selected from H, C₁-C₄ alkyl andC₁-C₄ haloalkyl; and wherein any two substituents on neighbouring atomsand comprising R^(a) groups may join up to form a ring.

In an embodiment, in any R¹-R²² group which contains an alkyl,haloalkyl, cycloalkyl, or heterocycloalkyl group, that alkyl, haloalkyl,cycloalkyl or heterocycloalkyl group is optionally substituted, wherechemically possible, by 1 to 4 substituents which are each independentlyselected at each occurrence from the group consisting of: oxo; ═NR^(a);═NOR²; R²; halo; nitro; cyano; NR^(a)R^(a); SO₃R^(a); SO₂R^(a);SO₂NR^(a)R^(a); CO₂R^(a); C(O)R^(a); CONR^(a)R^(a); CH₂NR^(a)R^(a);CH₂OR^(a); and OR^(a); wherein R^(a) is selected from H, C₁-C₄ alkyl andC₁-C₄ haloalkyl.

A group which is represented as SO₃R is typically a group having theform S(O)₂OR. A group which is represented as S(O)₂R is typically agroup having the form S(O)₂R. A group which is represented asSO₂NR^(a)R^(a) is typically a group having the form S(O)₂NRR.

Compounds of the invention containing one or more asymmetric carbonatoms can exist as two or more stereoisomers. Where a compound of theinvention contains a double bond such as a C═C or C═N group, geometriccis/trans (or Z/E) isomers are possible. Where structural isomers areinterconvertible via a low energy barrier, tautomeric isomerism(‘tautomerism’) can occur. This can take the form of proton tautomerismin compounds of the invention containing, for example, an imino, keto,or oxime group, or so-called valence tautomerism in compounds whichcontain an aromatic moiety. It follows that a single compound mayexhibit more than one type of isomerism.

Included within the scope of the present invention are allstereoisomers, geometric isomers and tautomeric forms of the compoundsof the invention, including compounds exhibiting more than one type ofisomerism, and mixtures of one or more thereof. Also included are acidaddition or base salts wherein the counter ion is optically active, forexample, d-lactate or 1-lysine, or racemic, for example, dl-tartrate ordl-arginine.

The compounds of the invention may be obtained, stored and/or used inthe form of an agronomically acceptable salt. Suitable salts include,but are not limited to, salts of acceptable inorganic acids such ashydrochloric, sulphuric, phosphoric, nitric, carbonic, boric, sulfamic,and hydrobromic acids, or salts of agronomically acceptable organicacids such as acetic, propionic, butyric, tartaric, maleic,hydroxymaleic, fumaric, malic, citric, lactic, mucic, gluconic, benzoic,succinic, oxalic, phenylacetic, methanesulphonic, toluenesulphonic,benzenesulphonic, salicylic, sulphanilic, aspartic, glutamic, edetic,stearic, palmitic, oleic, lauric, pantothenic, tannic, ascorbic andvaleric acids. Suitable salts also include salts of inorganic andorganic bases, e.g. counterions such as Na, Ca, K, Li, Mg, ammonium,trimethylsulfonium. The compounds may also be obtained, stored and/orused in the form of an N-oxide.

Cis/trans isomers may be separated by conventional techniques well knownto those skilled in the art, for example, chromatography and fractionalcrystallisation.

Conventional techniques for the preparation/isolation of individualenantiomers when necessary include chiral synthesis from a suitableoptically pure precursor or resolution of the racemate (or the racemateof a salt or derivative) using, for example, chiral high pressure liquidchromatography (HPLC). Thus, chiral compounds of the invention (andchiral precursors thereof) may be obtained in enantiomerically-enrichedform using chromatography, typically HPLC, on an asymmetric resin with amobile phase consisting of a hydrocarbon, typically heptane or hexane,containing from 0 to 50% by volume of isopropanol, typically from 2% to20%, and for specific examples, 0 to 5% by volume of an alkylamine e.g.0.1% diethylamine. Concentration of the eluate affords the enrichedmixture.

Alternatively, the racemate (or a racemic precursor) may be reacted witha suitable optically active compound, for example, an alcohol, or, inthe case where the compound of the invention contains an acidic or basicmoiety, a base or acid such as 1-phenylethylamine or tartaric acid. Theresulting diastereomeric mixture may be separated by chromatographyand/or fractional crystallization and one or both of thediastereoisomers converted to the corresponding pure enantiomer(s) bymeans well known to a skilled person.

When any racemate crystallises, crystals of two different types arepossible. The first type is the racemic compound (true racemate)referred to above wherein one homogeneous form of crystal is producedcontaining both enantiomers in equimolar amounts. The second type is theracemic mixture or conglomerate wherein two forms of crystal areproduced in equimolar amounts each comprising a single enantiomer.

While both of the crystal forms present in a racemic mixture haveidentical physical properties, they may have different physicalproperties compared to the true racemate. Racemic mixtures may beseparated by conventional techniques known to those skilled in theart—see, for example, “Stereochemistry of Organic Compounds” by E. L.Eliel and S. H. Wilen (Wiley, 1994).

The activity of the compounds of the present invention can be assessedby a variety of in silico, in vitro and in vivo assays. In silicoanalysis of a variety of compounds has been demonstrated to bepredictive of ultimate in vitro and even in vivo activity.

The present invention also includes all environmentally acceptableisotopically-labelled compounds of formulae I to XXIX and theirsyntheses, wherein one or more atoms are replaced by atoms having thesame atomic number, but an atomic mass or mass number different from theatomic mass or mass number usually found in nature.

Examples of isotopes suitable for inclusion in the compounds of theinvention include isotopes of hydrogen, such as ²H and ³H, carbon, suchas ¹¹C, ¹³C and ¹⁴C, chlorine, such as ³⁶Cl, fluorine, such as ¹⁸F,iodine, such as ¹²³I and ¹²⁵I, nitrogen, such as ¹³N and ¹⁵N, oxygen,such as ¹⁵O, ¹⁷O and ¹⁸O, phosphorus, such as ³²P, and sulphur, such as³⁵S.

Isotopically-labelled compounds can generally be prepared byconventional techniques known to those skilled in the art or byprocesses analogous to those described using an appropriateisotopically-labelled reagent in place of the non-labelled reagentpreviously employed.

Throughout this specification these abbreviations have the followingmeanings:

DCE—dichloromethane DCM—dichloromethane

DMAP—N,N-dimethyl-4-aminopyridine DMF—dimethylformamide

DMSO—dimethylsulfoxide mCPBA—meta-chloroperbenzoic acid

THF—tetrahydrofuran TLC—thin layer chromatography

TMS—trimethylsilyl

Throughout the description and claims of this specification, the words“comprise” and “contain” and variations of the words, for example“comprising” and “comprises”, means “including but not limited to”, andis not intended to (and does not) exclude other moieties, additives,components, integers or steps.

Throughout the description and claims of this specification, thesingular encompasses the plural unless the context otherwise requires.In particular, where the indefinite article is used, the specificationis to be understood as contemplating plurality as well as singularity,unless the context requires otherwise.

Features, integers, characteristics, compounds, chemical moieties orgroups described in conjunction with a particular aspect, embodiment orexample of the invention are to be understood to be applicable to anyother aspect, embodiment or example described herein unless incompatibletherewith.

If appropriate, the compounds of the invention can, at certainconcentrations or application rates, be used as herbicides.

According to another aspect of the present invention, there is provideda method for controlling the weeds, the method comprising applying anagronomically effective and substantially non-phytotoxic (to the cropplant) quantity of a compound according to the invention to the plantsthemselves or to the area where it is intended that the plants willgrow.

The pesticide may be applied as a foliar application, stem application,drench or drip application (chemigation) to the plant or to the fruit ofthe plant or to soil or to inert substrate (e.g. inorganic substrateslike sand, rockwool, glasswool; expanded minerals like perlite,vermiculite, zeolite or expanded clay), Pumbe, Pyroclastic materials orstuff, synthetic organic substrates (e.g. polyurethane) organicsubstrates (e.g. peat, composts, tree waste products like coir, woodfibre or chips, tree bark) or to a liquid substrate (e.g. floatinghydroponic systems, Nutrient Film Technique, Aeroponics).

In a further aspect, the present invention also relates to a herbicidalcomposition comprising an effective amount of an active compound of theinvention. The composition may further comprise one or more additionalherbicides.

The term “effective and non-phytotoxic amount” means an amount ofpesticide according to the invention which is sufficient to control ordestroy any of the targeted pests present or liable to appear in thecrops and which does not have any significant detrimental effect on thecrops or indeed has a positive effect on plant vigour and yield in theabsence of target organism. The amount will vary depending on the pestto be controlled, the type of crop, the climatic conditions and thecompounds included in the pesticidal composition. This amount can bedetermined by systematic field trials, which are within the capabilitiesof a person skilled in the art.

Depending on their particular physical and/or chemical properties, theactive compounds of the invention can be formulated as solutions,emulsions, suspensions, powders, foams, pastes, granules, aerosols,microencapsulations in polymeric substances and also as ULV cold andwarm fogging formulations.

The active compounds can be used neat, or in the form of a formulation,e.g. ready-to-use solutions, emulsions, water- or oil-based suspensions,powders, wettable powders, pastes, soluble powders, dusts, solublegranules, granules for broadcasting, suspoemulsion concentrates, naturalsubstances impregnated with active compound, synthetic substancesimpregnated with active compound, fertilizers and alsomicroencapsulations in polymeric substances. Application may be carriedout, for example, by watering, spraying, atomizing, broadcasting,dusting, foaming, spreading, etc. It is also possible to apply theactive compounds by the ultra-low volume method or to inject thepreparation of active compound or the active compound itself into thesoil.

Formulations containing the compounds of the invention are produced in aknown manner, for example by mixing the compounds with extenders (e.g.liquid solvents and/or solid carriers), optionally with the use ofsurfactants (e.g. emulsifiers and/or dispersants and/or foam-formers).The formulations are prepared either in factories/production plants oralternatively before or during the application.

Auxiliaries are substances which are suitable for imparting to thecomposition itself and/or to preparations derived therefrom (for examplespray liquors) particular properties such as certain technicalproperties and/or also particular biological properties. Typicalsuitable auxiliaries are: extenders, solvents and carriers.

Suitable extenders are, for example, water, polar and nonpolar organicchemical liquids, for example from the classes of the aromatic andnon-aromatic hydrocarbons (such as paraffins, alkylbenzenes,alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, ifappropriate, may also be substituted, etherified and/or esterified), theketones (such as acetone, cyclohexanone), esters (including fats andoils) and (poly)ethers, the unsubstituted and substituted amines,amides, lactams (such as N-alkylpyrrolidones) and lactones, thesulphones and sulphoxides (such as dimethyl sulphoxide).

If the extender used is water, it is also possible to use, for example,organic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, alcohols such as butanol or glycol and also their ethers andesters, ketones such as acetone, methyl ethyl ketone, methyl isobutylketone or cyclohexanone, strongly polar solvents such asdimethylformamide and dimethyl sulphoxide.

Suitable solid carriers are: for example, ammonium salts and groundnatural minerals such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and silicates; suitablesolid carriers for granules are: for example, crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,and also synthetic granules of inorganic and organic meals, and granulesof organic material such as paper, sawdust, coconut shells, maize cobsand tobacco stalks; suitable emulsifiers and/or foam-formers are: forexample, nonionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonatesand also protein hydrolysates; suitable dispersants are nonionic and/orionic substances, for example from the classes of the alcohol-POE and/or-POP ethers, acid and/or POP-POE esters, alkylaryl and/or POP-POEethers, fat- and/or POP-POE adducts, POE- and/or POP-polyol derivatives,POE- and/or POP-sorbitan- or -sugar adducts, alkyl or aryl sulphates,alkyl- or arylsulphonates and alkyl or aryl phosphates or thecorresponding PO-ether adducts. Furthermore, suitable oligo- orpolymers, for example those derived from vinylic monomers, from acrylicacid, from EO and/or PO alone or in combination with, for example,(poly)alcohols or (poly)amines. It is also possible to employ lignin andits sulphonic acid derivatives, unmodified and modified celluloses,aromatic and/or aliphatic sulphonic acids and their adducts withformaldehyde.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations.

Further additives may be mineral and vegetable oils. It is also possibleto add colorants such as inorganic pigments, for example iron oxide,titanium oxide and Prussian Blue, and organic dyestuffs, such asalizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc. Other possible additives are perfumes,mineral or vegetable, optionally modified oils and waxes.

The formulations may also comprise stabilizers, e.g. low-temperaturestabilizers, preservatives, antioxidants, light stabilizers or otheragents which improve chemical and/or physical stability.

The formulations generally comprise between 0.01 and 98% by weight ofactive compound, preferably between 0.1 and 95% and particularlypreferably between 0.5 and 90%.

The active compounds according to the invention can also be used as amixture with other known herbicides for example, to improve the activityspectrum or to reduce or slow the development of resistance.

A mixture with other known active compounds such as nematicides,acaricides, fungicides, insecticides or bactericides, or withfertilizers and growth regulators, safeners or semiochemicals is alsopossible.

Exemplary application rates of the active compounds according to theinvention are: when treating leaves: from 0.1 to 10 000 g/ha, preferablyfrom 10 to 1000 g/ha, particularly preferably from 50 to 300 g/ha (whenthe application is carried out by watering or dripping, it is evenpossible to reduce the application rate, especially when inertsubstrates such as rock wool or perlite are used); when treating thesoil: from 0.1 to 10 000 g/ha, preferably from 1 to 5000 g/ha.

A formulation which could be used to administer the compounds,particularly in the context of testing for activity, would be to supplyall compounds as a 10% solution in DMSO. If there are solubilityproblems this can be helped by adding acetone (e.g. to dilute a DMSOsolution/suspension by 50% resulting in a 5% solution of the compound inDMSO/acetone. The administration formulation is then obtained by addingthe DMSO (or DMSO/acetone) solution to a 0.1% solution of Tween 20™ inwater to give the required concentration. The result is likely to be anemulsion that can be sprayed. If crystallisation occurs, resulting ininconsistent results, further DMSO can be added to the test solution.

The compositions according to the invention are suitable for protectingany plant variety which is employed in agriculture, in the greenhouse,in forests or in horticulture and, in particular, cereals (e.g. wheat,barley, rye, millet and oats), maize, cotton, soya beans, rice,potatoes, sunflowers, beans, coffee, beet (for example sugar beet andfodder beet), peanuts, vegetables (e.g. tomatoes, cucumbers, onions andlettuce), lawns, fruit and nut trees (e.g. apples pears peachesnectarines, apricots, hazelnut, pecan, macadamia, pistachio), soft fruit(e.g. strawberries, raspberries, blackcurrants, redcurrants),grapevines, bananas, cocoa and ornamental plants.

The active compounds of the invention, in combination with good planttolerance and favourable toxicity to warm-blooded animals and beingtolerated well by the environment, are suitable for protecting plantsand plant organs, for increasing the harvest yields, for improving thequality of the harvested material and for controlling animal pests, inparticular nematodes, which are encountered in agriculture, inhorticulture, in animal husbandry, in forests, in gardens and leisurefacilities, in the protection of stored products and of materials, andin the hygiene sector. They may be preferably employed as cropprotection agents.

Use as Herbicides

Some compounds of the invention may also have herbicidal activityagainst a broad spectrum of economically important mono- anddicotyledonous harmful plants. Some compounds of the invention may haveherbicidal activity against monocotyledonous plants but no activity orlittle activity against dicotyledonous crops. Other compounds of theinvention may be selective, having excellent herbicidal activity againstdicotyledonous plants but no activity or little activity againstmonocotyledonous crops.

Difficult-to-control perennial weeds which produce shoots from rhizomes,root stocks or other perennial organs may also be controlled byherbicidal compounds. Here, the substances can be applied by thepre-sowing method, the pre-emergence method and/or the post-emergencemethod.

The following are illustrative examples of monocotyledonous weeds thatmay be controlled by herbicidal compounds: Avena spp., Alopecurus spp.,Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicumspp., Phalaris spp., Poa spp., Setaria spp. and also Bromus spp. such asBromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorumand Bromus japonicus and Cyperus species from the annual group, and,Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperusspecies, from the perrenial group.

The following are illustrative examples of dicotyledonous weeds that maybe controlled by herbicidal compounds: Abutilon spp., Amaranthus spp.,Chenopodium spp., Chrysanthemum spp., Galium spp. such as Galiumaparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp.,Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp.,Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., in the caseof annuals, and Convolvulus, Cirsium, Rumex and Artemisia in the case ofthe perennials.

If herbicidal compounds are applied to the soil surface before or duringgermination, the weed seedlings are inhibited or prevented completelyfrom emerging or else the weeds grow until they have reached thecotyledon stage, but then their growth stops, and, eventually, they diecompletely.

If herbicidal compounds are applied post-emergence to the green parts ofthe plants, growth typically stops following the treatment, and the weedplants remain substantially at the growth stage of the point of time ofapplication, or they die completely, so that in this manner competitionfrom the weeds is eliminated quickly and in a sustained manner.

DETAILED DESCRIPTION Synthesis

The skilled man will appreciate that adaptation of methods known in theart could be applied in the manufacture of the compounds of the presentinvention.

For example, the skilled person will be immediately familiar withstandard textbooks such as “Comprehensive Organic Transformations—AGuide to Functional Group Transformations”, R C Larock, Wiley-VCH (1999or later editions); “March's Advanced Organic Chemistry—Reactions,Mechanisms and Structure”, M B Smith, J. March, Wiley, (5th edition orlater); “Advanced Organic Chemistry, Part B, Reactions and Synthesis”, FA Carey, R J Sundberg, Kluwer Academic/Plenum Publications, (2001 orlater editions); “Organic Synthesis—The Disconnection Approach”, SWarren (Wiley), (1982 or later editions); “Designing Organic Syntheses”S Warren (Wiley) (1983 or later editions); “Heterocyclic Chemistry”, J.Joule (Wiley 2010 edition or later); (“Guidebook To Organic Synthesis” RK Mackie and D M Smith (Longman) (1982 or later editions), etc., and thereferences therein as a guide.

The skilled person is familiar with a range of strategies forsynthesising organic and particularly heterocyclic molecules and theserepresent common general knowledge as set out in text books such asWarren “Organic Synthesis: The Disconnection Approach”; Mackie and Smith“Guidebook to Organic Chemistry”; and Clayden, Greeves, Warren andWothers “Organic Chemistry”.

The skilled chemist will exercise his judgement and skill as to the mostefficient sequence of reactions for synthesis of a given target compoundand will employ protecting groups as necessary. This will depend interalia on factors such as the nature of other functional groups present ina particular substrate. Clearly, the type of chemistry involved willinfluence the choice of reagent that is used in the said syntheticsteps, the need, and type, of protecting groups that are employed, andthe sequence for accomplishing the protection/deprotection steps. Theseand other reaction parameters will be evident to the skilled person byreference to standard textbooks and to the examples provided herein.

Sensitive functional groups may need to be protected and deprotectedduring synthesis of a compound of the invention. This may be achieved byconventional methods, for example as described in “Protective Groups inOrganic Synthesis” by TW Greene and PGM Wuts, John Wiley & Sons Inc(1999), and references therein.

Certain compounds of the invention can be made according to thefollowing general synthetic schemes. Certain compounds of the inventioncan be made according to or analogously to the methods described inExamples 1 to 4.

General Synthetic Schemes

A metallation reaction (e.g. using (^(i)PrO)₄Ti and ^(i)PrMgCloptionally in ether at room temperature) on alkyne A followed byconjugate addition to alkene B can provide compound C. Removal of theTMS protecting group (e.g. using K₂CO₃ optionally in methanol at roomtemperature) followed by decarboxylation (for compounds in which R¹⁶ isMe or Et this reaction can be conducted in the presence of LiCl in DMSOat 150° C.) can provide alkyne D. Compounds in which R¹⁶ is H cantypically be made according to this route using a methyl or ethyl esterand then hydrolysing that ester (e.g. using NaOH and water optionally inTHF at room temperature) to generate the carboxylic acid. This route isparticularly useful for compounds of formula IX, examples of which arecompounds 1 and 2:

Compounds of formula E can be synthesised as described in WO2011/098417.Ester hydrolysis (e.g. using NaOH and water optionally in THF at roomtemperature) can generate the carboxylic acid F. Acid F can be convertedto the acid chloride (e.g. using SOCl₂) which can undergo reaction withorganozinc agent G to form the ketone H. Alternatively, acid F can beconverted to a mixed anhydride (e.g. using ClCO₂Me and triethylamineoptionally in THF at room temperature) which upon reduction (e.g. usingNaBH₄ in ethanol optionally at room temperature) can provide an alcoholwhich can be alkylated using alkylating agent J (e.g. using NaNH₂optionally in Et₂O at room temperature) to provide ether K. This routeis particularly useful for compounds of formulae X and XI, examples ofwhich are compounds 3 and 4:

An aldol like reaction (e.g. using CeCl₃ optionally in THF at roomtemperature, followed by BuLi optionally in Et₂O and THF at roomtemperature with an acidic work up) between nitrile L and aldehyde Mcan, once the product has been acylated with acyl chloride N (e.g. usingDMAP and triethylamine optionally in DCM at room temperature), providecompounds of formula O. This route is particularly useful for compoundsof formula XIV, an example of which is compound 5:

An alternative set of reaction conditions (e.g. NaOMe optionally inethanol at room temperature) can be used to convert L and M tocondensation product P. Addition of ammonia (e.g. in isopropanol at roomtemperature) can provide amine Q. Subsequent acylation with acylchloride N or chloroformate S (e.g. using DMAP and triethylamineoptionally in DCM at room temperature), can provide compounds of formulaR or T respectively. This route is particularly useful for compounds offormulae XII and XIII, examples of which are compounds 6 and 7:

Nitrile L can also react with epoxide U (e.g. through initialdeprotonation with BuLi optionally in THF at −78° C. followed by NH₄Clwork up) to generate an alcohol which, upon mesylation (e.g. withMeSO₂Cl and NEt₃ optionally in DCM at 0° C.), can provide mesylate W.Displacement of the mesylate with tBuSH (e.g. in the presence of Cs₂CO₃optionally in MeCN at reflux) can, following oxidation (e.g. using mCPBAoptionally in DCM and water at room temperature), provide compounds offormula Yin which R¹⁶ is H. Alternatively, displacement with Na₂SO₃(optionally in water at room temperature) can provide compounds offormula Z. In yet another alternative, displacement with a phosphite(i.e. P(OR¹⁶)₃ with the reaction optionally conducted in the presence ofBu₄NI at 150° C.) can provide compounds of formula AA. For compounds offormula AA in which R¹⁶ is H the compounds may preferably be made byreacting W with a trialkylphosphite (e.g. P(OMe)₃) and subsequentlyhydrolysing the phosphate ester groups (e.g. using TMSBr andTMSCH₂CH═CH₂ at room temperature followed by NH₄HCO₃). This route isparticularly useful for compounds of formulae XV, XVI and XVII, examplesof which are compounds 8, 9 and 10:

A reductive amination reaction between amine AB and aldehyde AC (e.g.using NaBH₃CN optionally in methanol at room temperature) can provideamine AD. Reaction between amine AB and sulfonyl chloride AE (e.g. inpyridine optionally at room temperature) can provide sulphonamide AF.This route is particularly useful for compounds of formula XIX examplesof which are compounds 11 to 14:

Treatment of chloride AG with compound AH (e.g. using NaH optionally inTHF at room temperature) can provide AI. Subsequent deprotection (e.g.with N₂H₄ optionally in ethanol at room temperature) can providehydroxylamine AJ. Condensation between aldehyde AC and hydroxylamine AJcan provide oxime AK. This route is particularly useful for compounds offormula XIX, examples of which are compounds 15 and 16:

The route described in Scheme G can also be used, with the appropriatestarting chloride to prepare the compounds of formula XX, an example ofwhich is compound 17:

A condensation reaction (e.g. in ethanol at 80° C.) between amine AL andaldehyde AC can provide imine AM. This route is particularly useful forcompounds of formula XX, an example of which is compound 18:

Alkylation of amine AN with chloride AO (e.g. using KOH optionally inmethanol at room temperature) can provide a compound which can becyclised (e.g. using acetic acid and NaOAc optionally at roomtemperature) to form compounds of formula AP. This route is particularlyuseful for compounds of formula XXI, examples of which are compounds 19and 20:

A condensation/cyclisation (e.g. using POCl₃ optionally at 100° C.)between diamine AQ and carboxylic acid AR can provide fused imidazoleAS. This route is particularly useful for compounds of formula XXI, anexample of which is compound 21:

EXAMPLES

Flash chromatography was carried out using silica gel (40-63 μmparticles). Thin layer chromatography was carried out on pre-coatedaluminium backed plates (Merck silica Keiselgel 60 F₂₅₄). Visualisationwas carried out with UV light (254 nm) and by staining with eitherpotassium permanganate, phosphomolybdic acid (PMA) or ninhydrinsolutions. Where hexane is specified as a flash chromatography solvent,petroleum ether (b.p. 40-60° C.) can be used as an alternative.

All ¹H NMR spectra were obtained using either a Bruker Ultrashield 300spectrometer or Bruker DPX300 spectrometer. Chemical shifts areexpressed in parts per million (δ) and are referenced to the solvent.Coupling constants J are expressed in Hertz (Hz).

ESI mass spectrometry was performed using a Bruker HCT Ultra LCMSinstrument (Agilent 1200 Series LC with diode array detector and BrukerHCT Ultra Ion Trap MS) using a Phenomenex Luna 5u C18(2) 100 Å, 50×2.00mm 5 micron LC column (solvent: 5-90% gradient of acetonitrile in water(with 1% formic acid). Flow rate 1.2 mL/min). EI mass spectrometry wasperformed using a Varian Saturn 2100T GC/MS instrument with a FactorFourVF-5MS 30 m×0.25 mm capillary column. High resolution mass spectrometry(ESI) was performed using a Dionex UltiMate 3000 system.

All reagents were obtained from commercial suppliers and used assupplied unless otherwise stated.

Example 11-[4-Chloro-2-fluoro-5-[(E)-(isopropyl(methyl)sulfamoyl)iminomethyl]phenyl]-3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidine22

2-[Methyl(sulfamoyl)amino]propane (217 mg, 1.43 mmol) was added to asuspension of2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzaldehyde(WO 97/30060; EP 542685; 500 mg, 1.43 mmol) in toluene (5 mL) undernitrogen in the presence of QuadraPure™ SA and molecular sieves. Thereaction mixture was heated at reflux for 20 hours before addition of afurther portion of 2-[methyl(sulfamoyl)amino]propane (40 mg, 0.26 mmol).The heating was continued for a further 4 hours, after which time TLCshowed complete consumption of the starting aldehyde. The reactionmixture was filtered through celite and the resulting filtrate was driedin vacuo. The crude material was purified by flash chromatography onsilica gel (solvent 75:25 hexane/EtOAc) to afford the product as acolourless oil (124 mg, 18%).

NMR δ_(H) (CDCl₃, 300 MHz): 9.17 (s, 1H), 8.03 (d, J=7.5 Hz, 1H), 7.35(d, J=9.0 Hz, 1H), 6.31 (s, 1H), 4.23-4.14 (m, 1H), 3.50 (s, 3H), 2.68(s, 3H), 1.09 (d, J=7.5 Hz, 6H). ESI-MS 485.0 [MH]⁺.

1-[4-Chloro-2-fluoro-5-[[(isopropyl(methyl)sulfamoyl)amino]methyl]phenyl]-3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidine23

2-[Methyl(sulfamoyl)amino]propane (211 mg, 1.39 mmol) was added to asuspension of2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzaldehyde(486 mg, 1.39 mmol) in toluene (5 mL) under nitrogen in the presence ofmolecular sieves. The reaction mixture was heated at reflux for 21hours, after which time TLC showed complete consumption of the startingaldehyde. The reaction mixture was filtered through celite and theresulting filtrate was dried in vacuo to afford the imine product as abrown residue (640 mg). Sodium (triacetoxy)borohydride (1.47 g, 6.95mmol) was added to a portion of the imine (500 mg) in DCE (5 mL) undernitrogen in the presence of molecular sieves. The reaction mixture wasstirred at ambient temperature for 18 hours, after which time TLC showedcomplete consumption of the imine. 2 M HCl_((aq)) (20 mL) was added andthe reaction mixture was extracted with DCM (3×25 mL) and then theorganics were washed with brine (3×25 mL) before being dried over MgSO₄and the solvent removed in vacuo. The crude material was purified byflash chromatography on silica gel (solvent 65:35 hexane/EtOAc) toafford the product as a yellow solid (194 mg).

NMR δ_(H) (CDCl₃, 300 MHz): 7.37 (d, J=7.5 Hz, 1H), 7.23 (d, J=9.0 Hz,1H), 6.23 (s, 1H), 4.76 (t, J=6.5 Hz, 1H), 4.17 (d, J=6.5 Hz, 2H), 4.02(sept, J=6.5 Hz, 1H), 3.50 (s, 3H), 2.57 (s, 3H), 1.06 (d, J=6.5 Hz,6H). ESI-MS 487.1 [MH]⁺.

N-[[2-Chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]methyl]-3-methyl-butane-2-sulfonamide24

To ammonium hydroxide solution (28% NH₃ in H₂O, 75 mL) was added asolution of 3-methyl-2-butanesulfonyl chloride (3.90 g, 22.9 mmol) inchloroform (75 mL) dropwise and the mixture was stirred at roomtemperature for 1 h. The reaction mixture was diluted withtetrahydrofuran (25 mL) and extracted with chloroform (2×50 mL). Thecombined organic extracts were washed with brine (2×50 mL) and 2 Mhydrochloric acid (5 mL), dried over MgSO₄ and the solvent removed invacuo. The oil was purified by flash chromatography on silica gel(solvent 40% EtOAc/hexane) to afford 3-methylbutane-2-sulfonamide as abrown oil (0.68 g, 20%). ¹H NMR δ_(H) (CDCl₃, 300 MHz): 4.50 (br, 2H),2.94 (dq, J=7.1, 3.0 Hz, 1H), 2.43 (spt d, J=6.9, 2.8 Hz, 1H), 1.29 (d,J=7.0 Hz, 3H), 0.97 (m, 6H).

3-Methylbutane-2-sulfonamide (84 mg, 0.55 mmol) was added to asuspension of2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzaldehyde(175 mg, 0.50 mmol) in toluene (2 mL) under nitrogen in the presence ofmolecular sieves. The reaction mixture was heated at reflux for 72hours, after which time reaction mixture was filtered through celite andthe resulting filtrate was dried in vacuo to afford the imine product asa brown residue (200 mg). Sodium (triacetoxy)borohydride (106 g, 0.50mmol) was added to the imine in DCE (2 mL) under nitrogen in thepresence of molecular sieves. The reaction mixture was stirred atambient temperature for 72 hours, after which time TLC showed completeconsumption of the imine. 2 M HCl_((aq)) (10 mL) was added and thereaction mixture was extracted with EtOAc (3×20 mL) and then theorganics were washed with brine (3×25 mL) before being dried over MgSO₄and the solvent removed in vacuo. The crude material was purified byflash chromatography on silica gel (solvent 65:35 hexane/EtOAc) toafford the product as a yellow oil (137 mg, 56%).

NMR δ_(H) (CDCl₃, 300 MHz): 7.38 (dd, J=2.5, 7.5 Hz, 1H), 7.26 (d, J=9.0Hz, 1H), 6.24 (s, 1H), 4.75-4.66 (m, 1H), 4.32 (d, J=6.5 Hz, 1H), 3.45(s, 3H), 2.77-2.69 (m, 1H), 2.35-2.28 (m, 1H), 1.23-1.15 (m, 3H),0.95-0.85 (m, 6H). ESI-MS 486.1 [MH]⁺.

2-Chloro-4-fluoro-N-(isopropyl(methyl)sulfamoyl)-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzamide25

2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzoicacid was prepared according to the procedure provided in US2004/0018942. 2-[Methyl(sulfamoyl)amino]propane was prepared accordingto the procedure provided in US 2010/0216774. A solution of2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzoicacid (732 mg, 2 mmol) and carbonyldiimidazole (486 mg, 3 mmol) in THF(10 mL) was heated at reflux for 1 hour under nitrogen. After cooling toambient temperature, 2-[methyl(sulfamoyl)amino]propane (456 mg, 3 mmol)was added followed by 1,8-diazabicyclo[5.4.0]undec-7-ene (0.45 mL, 3mmol) and the reaction mixture was stirred at ambient temperature for 24hours, after which time TLC showed complete consumption of the startingmaterial. The reaction mixture was diluted with water (40 mL) and 2 MHCl_((aq)) (10 mL) and extracted with EtOAc (3×25 mL) and then theorganics were washed with brine (2×50 mL) before being dried over MgSO₄and the solvent removed in vacuo. The crude material was purified byflash chromatography on silica gel (solvent 60:40 hexane/EtOAc) toafford the title compound as a white solid (470 mg, 47%).

NMR δ_(H) (CDCl₃, 300 MHz): 9.12 (br, 1H), 7.71 (d, J=9.0 Hz, 1H), 7.40(d, J=9.0 Hz, 1H), 6.39 (s, 1H), 4.35-4.26 (m, 1H), 3.58 (s, 3H), 2.97(s, 3H), 1.22 (d, J=6.0 Hz, 6H). ESI-MS 501.0 [MH]⁺.

Compound 25 (saflufenacil) forms part of the prior art.

2-Chloro-N-(1,2-dimethylpropylsulfonyl)-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzamide26

Oxalyl chloride (85 μL, 1.0 mmol) was added to a solution of2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzoicacid (188 mg, 0.5 mmol) in DCM (2 mL) and DMF (1 drop) under nitrogen.After 1 hour, the volatiles were removed in vacuo and DMAP (88 mg, 0.7mmol), N,N-diisopropylethylamine (0.87 mL, 5.0 mmol) and toluene (1 mL)were added. A solution of 3-methylbutane-2-sulfonamide (302 mg, 2.0mmol) in toluene (2 mL) was added and the reaction was heated at refluxunder nitrogen for 20 hours, after which time TLC showed completeconsumption of the starting material. The reaction mixture was quenchedwith water (15 mL) and 2 M HCl_((aq)) (10 mL) and extracted with EtOAc(3×25 mL) and then the organics were washed with brine (2×25 mL) beforebeing dried over MgSO₄ and the solvent removed in vacuo. The crudematerial was purified by flash chromatography on silica gel (solvent 60%hexane/EtOAc) to afford the title compound as an off-white solid (152mg, 61% as a 1:1 mixture of diastereoisomers).

NMR δ_(H) (CDCl₃, 300 MHz): NMR δ_(H) (CDCl₃, 300 MHz): 9.30 (s, 0.5H),9.27 (s, 0.5H), 7.65 (d, 7.5 Hz, 0.5H), 7.64 (d, 7.5 Hz, 0.5H), 7.38 (s,0.5H), 7.35 (s, 0.5H), 6.23 (s, 1H), 3.77 (dq, J=7.1, 2.9 Hz, 1H), 3.62(s, 3H), 2.59 (spt d, J=6.9, 2.8 Hz, 1H), 1.38 (d, J=7.0 Hz, 3H), 1.08(d, J=6.9 Hz, 3H), 1.05 (d, J=6.6 HZ, 3H).

ESI-MS 500.1 [MH]⁺.

Example 2 Ethyl4-cyano-3-(2,6-difluorophenyl)-4-(4-fluorophenyl)butanoate 27

Ethyl (E)-3-(2,6-difluorophenyl)prop-2-enoate was prepared according tothe procedure provided in WO 2011126567. A solution of4-fluorophenylacetonitrile (1.27 g, 1.13 mL, 9.43 mmol) was addeddropwise over 5 minutes to a stirred suspension of potassiumtert-butoxide (1.06 g, 9.43 mmol) in tetrahydrofuran (40 mL) at −78° C.The mixture was stirred at −78° C. for 10 minutes and a solution ofethyl (E)-3-(2,6-difluorophenyl)prop-2-enoate (2.00 g, 9.43 mmol) intetrahydrofuran (4 mL) was added dropwise over 5 minutes to the mixture.The mixture was stirred at −78° C. for 1 hour before 2M aqueoushydrochloric acid (50 mL) and EtOAc (200 mL) were added to the mixture.The separated organic phase was washed with saturated aqueous sodiumhydrogen carbonate (50 mL) and brine (50 mL), dried over MgSO₄ andconcentrated in vacuo. The residue was purified by flash chromatographyon silica gel (solvent hexane moving to 25% EtOAc/hexane) to afford thetitle compound as a colourless oil (3.05 g, 93% containing a 2:1 mixtureof diastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.42-7.23 (m, 2H), 7.21-7.04 (m, 2.33H),6.96-6.90 (m, 2H), 6.75 (t, J=8.4 Hz, 0.67H), 4.28 (d, J=9.9 Hz, 0.67H),4.21-3.92 (m, 3H), 4.15 (s, 0.33H), 3.24-3.11 (m, 0.67H), 2.83 (dd,J=16.5 and 9.0 Hz, 0.67H), 2.67 (dd, J=16.2 and 6.0 Hz, 0.67H), 1.15 (t,J=7.2 Hz, 1H), 1.12 (t, J=7.2 Hz, 2H).

ESI-MS 370.0 [M+Na⁺].

Compound 27 forms part of the prior art (WO2013/010882) and is includedfor reference only.

4-Cyano-3-(2,6-difluorophenyl)-4-(4-fluorophenyl)butanoic acid 27a

A solution of ethyl4-cyano-3-(2,6-difluorophenyl)-4-(4-fluorophenyl)butanoate 27 (800 mg,2.30 mmol) and lithium hydroxide (61 mg, 2.53 mmol) in tetrahydrofuran(10 mL) and water (1 mL) was stirred at 45° C. for 6 hours. A furtherportion of lithium hydroxide (41 mg, 1.73 mmol) was added to themixture, and the mixture was then heated to 45° C. for 3 hours. Aftercooling to rt, water (50 mL) and dichloromethane (20 mL) were added tothe mixture and the separated aqueous phase was washed withdichloromethane (3×20 mL). The pH of the aqueous phase was adjusted topH 1 by dropwise addition of 2M aqueous hydrochloric acid and wasextracted with dichloromethane (3×40 mL). The combined organic fractionswere then dried over MgSO₄ and concentrated in vacuo to afford the titlecompound as a colourless oil which solidified on standing (656 mg, 89%containing a 1:1 ratio of diastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.39-7.23 (m, 2H), 7.21-7.02 (m, 2H), 6.93 (aprt, J=8.7 Hz, 2H), 6.73 (t, J=8.7 Hz, 1H), 4.24 (d, J=9.9 Hz, 0.5H),4.19-4.01 (m, 1H), 4.13 (s, 0.5H), 3.25 (dd, J=17.1 and 4.5 Hz, 0.5H),3.15 (dd, J=16.8 and 9.0 Hz, 0.5H), 2.88 (dd, J=17.1 and 8.4 Hz, 0.5H),2.73 (dd, J=16.8 and 6.0 Hz, 0.5H); ESI-MS 342.0 [M+Na⁺].

3-(2,6-Difluorophenyl)-2-(4-fluorophenyl)-5-hydroxy-pentanenitrile 28

A solution of borane tetrahydrofuran complex (2.35 mL, 2.35 mmol, 1.0Min tetrahydrofuran) was added dropwise over 15 minutes to a stirredsolution of 4-cyano-3-(2,6-difluorophenyl)-4-(4-fluorophenyl)butanoicacid 27 (500 mg, 1.57 mmol) in tetrahydrofuran (15 ml) and the mixturewas stirred at room temperature for 16 h. Methanol (10 mL) was carefullyadded dropwise over 15 minutes to the mixture and the mixture wasconcentrated in vacuo. The residue was re-dissolved in methanol (10 mL)and concentrated in vacuo with this process repeated three times. Theresidue was dissolved in a 1:1 mixture of EtOAc/petrol (50 mL) and theorganic phase was filtered through celite and silica, eluting with a 1:1mixture of EtOAc/petrol (100 mL) before the filtrate was concentrated invacuo. The residue was dissolved in EtOAc (100 mL) and the organic phasewas washed with water (25 mL), saturated aqueous sodium hydrogencarbonate (25 mL) and brine (25 mL), dried over MgSO₄ and concentratedin vacuo to afford the title compound as a colourless oil (478 mg, 100%containing a 1:1 mixture of diastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.43-7.23 (m, 1H), 7.20-7.04 (m, 3H), 7.01-6.83(m, 2H), 6.74 (apr t, J=8.7 Hz, 1H), 4.17 (d, J=9.0 Hz, 0.5H), 4.12 (d,J=11.4 Hz, 0.5H), 3.83-3.57 (m, 1H), 3.50-3.20 (m, 1H), 2.50-2.37 (m,0.5H), 2.26-2.10 (m, 0.5H), 1.96-1.85 (m, 0.5H), 1.75-1.65 (m, 0.5H),1.50 (br. s, 0.5H), 1.34 (br. s, 0.5H).

ESI-MS 306.0 [M⁺].

3-(2,6-Difluorophenyl)-2-(4-fluorophenyl)-5-hydroxy-2-methyl-pentanenitrile29

A solution of3-(2,6-difluorophenyl)-2-(4-fluorophenyl)-5-hydroxy-pentanenitrile 28(350 mg, 1.15 mmol) in tetrahydrofuran (2 mL) was added dropwise over 5minutes to a stirred suspension of sodium hydride (55 mg, 1.38 mmol, 60%dispersed in mineral oil) in tetrahydrofuran (10 mL) at 0° C. Themixture was stirred at 0° C. for 10 minutes before iodomethane (244 mg,0.11 mL, 1.72 mmol) was added dropwise over 2 minutes to the mixture.The mixture was warmed to room temperature and stirred for 16 h beforewater (50 mL) and EtOAc (50 mL) were added to the mixture. The separatedaqueous phase was extracted with EtOAc (2×50 mL) and the combinedorganic fractions were dried MgSO₄ and concentrated in vacuo. Theresidue was purified by flash chromatography on silica gel (solvent 10%EtOAc/hexane moving to 40% EtOAc/hexane) to afford the title compound asa colourless oil (124 mg, 34% containing a single diastereoisomer).

¹H NMR (300 MHz, CDCl₃): 7.39-7.25 (m, 2H), 7.22-7.08 (m, 1H), 7.01-6.88(m, 2H), 6.80-6.71 (m, 2H), 3.82 (dd, J=12.3 and 3.9 Hz, 1H), 3.74-3.62(m, 1H), 3.33 (td, J=10.2 and 4.9 Hz, 1H), 2.50-2.33 (m, 1H), 2.28-2.12(m, 1H), 1.93 (s, 3H), 1.57 (br. s, 1H).

ESI-MS 342.0 [M+Na⁺].

4-Cyano-3-(2,6-difluorophenyl)-4-(4-fluorophenyl)pentanoic acid 30

A solution of3-(2,6-difluorophenyl)-2-(4-fluorophenyl)-5-hydroxy-2-methyl-pentanenitrile29 (75 mg, 0.24 mmol) in chloroform (0.75 mL) and acetonitrile (0.75 mL)was added dropwise over 5 minutes to a stirred solution of sodiumperiodate (206 mg, 1.00 mmol) in water (1 mL) at room temperature.Ruthenium(III) chloride (5 mg, 0.03 mmol) was added in 1 portion to themixture and the mixture was then stirred at room temperature for 16 h.Water (10 mL) and EtOAc (10 mL) were added to the mixture and theseparated aqueous phase was extracted with EtOAc (3×10 mL) before thecombined organic fractions were dried over MgSO₄ and concentrated invacuo. The residue was purified by flash chromatography on silica gel(solvent 6% EtOAc/hexane) to afford the title compound as a colourlesssolid (55 mg, 71% containing a single diastereoisomer).

¹H NMR (300 MHz, CDCl₃): 7.38-7.25 (m, 2H), 7.24-7.12 (m, 1H), 6.98 (t,J=9.0 Hz, 2H), 6.84-6.69 (m, 2H), 4.09 (dd, J=10.2 and 4.8 Hz, 1H), 3.21(dd, J=16.8 and 10.2 Hz, 1H), 2.99 (dd, J=17.1 and 4.8 Hz, 1H), 1.88 (s,3H).

ESI-MS 356.2 [M+Na⁺].

2-Bromo-2-(2,6-difluorophenyl)ethanol 31

2-(2,6-Difluorophenyl)oxirane was prepared according to the procedureprovided in Dou et al. Bioorganic & Medicinal Chemistry (2010), 18(3),1093-1102. A biphasic solution of 2,6-difluorophenyl)oxirane (2.29 g,14.7 mmol) in hydrobromic acid (5 mL, 48% in water) and chloroform (40mL) was vigorously stirred at room temperature for 30 minutes. Water(100 mL) and dichloromethane (100 mL) were added to the mixture. Theseparated aqueous phase was extracted with dichloromethane (100 mL) andthe combined organic fractions were then washed with saturated aqueoussodium hydrogen carbonate (50 mL), dried over MgSO₄ and concentrated invacuo to afford the title compound as a light yellow oil (3.48 g, 100%).

¹H NMR (300 MHz, CDCl₃): 7.40-7.25 (m, 1H), 6.95 (apr t, J=8.4 Hz, 2H),5.43 (ddt, J=9.9, 6.0 and 1.5 Hz, 1H), 4.42-4.29 (m, 1H), 4.17-4.01 (m,1H), 2.16 (br. t, J=5.0, 1H).

[2-Bromo-2-(2,6-difluorophenyl)ethoxy]-tert-butyl-dimethyl-silane 32

tert-Butyldimethylsilyl chloride (2.37 g, 15.7 mmol) was added in oneportion to a stirred solution of 2-bromo-2-(2,6-difluorophenyl)ethanol31 (3.73 g, 15.7 mmol) and imidazole (1.28 g, 18.9 mmol) inN,N-dimethylformamide (4 mL) and the mixture was stirred at roomtemperature for 1 hour. Water (100 mL) and petrol (100 mL) were added tothe mixture. The separated aqueous phase was extracted with petrol (100mL) and the combined organic fractions were then dried over MgSO₄ andconcentrated in vacuo to afford the title compound as a light yellow oil(4.071 g, 74%).

¹H NMR (300 MHz, CDCl₃): 7.34-7.20 (m, 1H), 6.90 (apr t, J=8.4 Hz, 2H),5.32-5.26 (m, 1H), 4.27-4.13 (m, 2H), 0.80 (s, 9H), 0.06 (s, 3H), −0.02(s, 3H).

4-(tert-Butyl(dimethyl)silyl)oxy-3-(2,6-difluorophenyl)-2-(4-fluorophenyl)butanenitrile33

Potassium tert-butoxide (1.95 g, 17.4 mmol) was added in one portion toa stirred solution of 4-fluorophenylacetonitrile (2.35 g, 2.09 mL, 17.4mmol) and[2-bromo-2-(2,6-difluorophenyl)ethoxy]-tert-butyl-dimethyl-silane 32(4.07 g, 11.6 mmol) in tetrahydrofuran (50 mL) and the mixture washeated to 50° C. for 5 hours. Water (250 mL) and petrol (150 mL) wereadded to the mixture. The separated aqueous phase was extracted withpetrol (150 mL) and the combined organic fractions were then dried overMgSO₄ and concentrated in vacuo. The residue was purified by flashchromatography on silica gel (solvent hexane moving to 4% EtOAc/hexane)to afford the title compound as a light yellow oil (4.92 g, 78%containing a 3:2 mixture of diastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.39-7.29 (m, 1H), 7.25-7.16 (m, 1H), 7.16-7.03(m, 2H), 6.97-6.84 (m, 2H), 6.73 (t, J=9.0 Hz, 1H), 4.62 (d, J=9.0 Hz,0.4H), 4.27-4.06 (m, 0.8H), 4.14 (d, J=6.0 Hz, 0.6H), 3.97-3.62 (m,1.2H), 0.82 (s, 3.6H), 0.81 (s, 5.4H), 0.02 (s, 1.8H), −0.05 (s, 1.8H),−0.08 (s, 1.2H), −0.10 (s, 1.2H).

ESI-MS 406.2 [M+H⁺].

3-(2,6-Difluorophenyl)-2-(4-fluorophenyl)-4-hydroxy-butanenitrile 34

A solution of hydrogen fluoride pyridine (1.07 mL, 7.39 mmol, −70%hydrogen fluoride) was added dropwise over 10 minutes to a stirredsolution of4-(tert-butyl(dimethyl)silyl)oxy-3-(2,6-difluorophenyl)-2-(4-fluorophenyl)butanenitrile33 (2.50 g, 6.16 mmol) in tetrahydrofuran (40 mL) at room temperature ina plastic container. The mixture was stirred at room temperature for 16h before saturated aqueous sodium hydrogen carbonate (200 mL) wascarefully added dropwise over 1 hour to the mixture followed by EtOAc(100 mL). The separated aqueous phase was extracted with EtOAc (100 mL)and the combined organic fractions were washed with water (50 mL), 0.5Maqueous hydrochloric acid (50 mL), saturated aqueous sodium hydrogencarbonate (50 mL) and brine (50 mL) before being dried over MgSO₄ andconcentrated in vacuo. The residue was purified by flash chromatographyon silica gel (solvent hexane moving to 30% EtOAc/hexane) to afford thetitle compound as a colourless oil (1.70 g, 95% containing a 3:2 mixtureof diastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.42-7.24 (m, 1H), 7.23-7.05 (m, 2.8H),7.01-6.88 (m, 2H), 6.78 (t, J=8.7 Hz, 1.2H), 4.54 (d, J=9.6 Hz, 0.4H),4.41-4.08 (m, 1.4H), 4.28 (d, J=11.1 Hz, 0.6H), 3.98-3.71 (m, 1.6H),1.76 (t, J=6.0 Hz, 0.6H), 1.57 (t, J=6.0 Hz, 0.4H).

ESI-MS 292.0 [M+H⁻].

3-(2,6-difluorophenyl)-2-(4-fluorophenyl)-3-hydroxy-propanenitrile 35

A solution of 4-fluorophenylacetonitrile (1.35 g, 10.0 mmol) was addeddropwise over 5 minutes to a stirred suspension of potassiumtert-butoxide (1.12 g, 10.0 mmol) in tetrahydrofuran (20 mL) at −78° C.The mixture was stirred at −78° C. for 10 minutes before a solution of2,6-difluorobenzaldehyde (1.42 g, 10.0 mmol) in tetrahydrofuran (2 mL)was added dropwise over 5 minutes to the mixture. The mixture wasstirred at −78° C. for 1 hour before 2M aqueous hydrochloric acid (50mL) and EtOAc (200 mL) were added to the mixture. The separated organicphase was washed with saturated aqueous sodium hydrogen carbonate (50mL) and brine (50 mL), dried over MgSO₄ and concentrated in vacuo. Theresidue was purified by flash chromatography on silica gel (solvent 10%EtOAc/hexane) to afford the title compound as a colourless oil whichsolidified on standing (2.25 g, 81% containing a 3:2 mixture ofdiastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.42-7.28 (m, 1H), 7.27-7.06 (m, 2.8H), 6.95(apr t, J=8.4 Hz, 2H), 6.83 (apr t, J=8.4 Hz, 1.2H), 5.35-5.32 (m, 1H),4.37 (d, J=8.4 Hz, 0.4H), 4.36 (d, J=9.0 Hz, 0.6H), 3.05 (br. s, 0.6H),2.64 (br. s, 0.4H).

ESI-MS 300.0 [M+Na⁺].

Ethyl3-(2,6-difluorophenyl)-4-(4-fluorophenyl)-6-trimethylsilyl-hex-5-ynoate36

3-(4-Fluorophenyl)prop-1-ynyl-trimethyl-silane was prepared according tothe process provided in WO 2011/034832. A solution of3-(4-fluorophenyl)prop-1-ynyl-trimethyl-silane (615 mg, 3.0 mmol) in THF(4 mL) was cooled to −78° C. and treated with potassium tert-butoxide(335 mg, 3.0 mmol) in one portion. The mixture was stirred for 10minutes before a solution of ethyl(E)-3-(2,6-difluorophenyl)prop-2-enoate (633 mg, 3.0 mmol) in THF (4 mL)was added dropwise. The mixture was stirred for 1 h before 2N HCl (4 mL)and EtOAc (4 mL) were added and the mixture allowed to come to RT over16 h. The organic layer was separated, the aqueous layer was extractedwith EtOAc (2×10 mL), the combined organics dried over MgSO₄ and thesolvent removed in vacuo. The residue was purified by flashchromatography on silica gel (solvent hexane moving to 5% EtOAc/hexane)to afford the title compound contaminated with ethyl3-(2,6-difluorophenyl)-4-(4-fluorophenyl)hex-5-ynoate (620 mg) Thematerial was taken forward into future reactions without furtherpurification.

Ethyl 3-(2,6-difluorophenyl)-4-(4-fluorophenyl)hex-5-ynoate 37

A solution of ethyl3-(2,6-difluorophenyl)-4-(4-fluorophenyl)-6-trimethylsilyl-hex-5-ynoate36 (500 mg, 1.20 mmol) and potassium carbonate (165 mg, 1.20 mmol) inethanol (10 mL) was stirred at room temperature overnight. The mixturewas concentrated in vacuo and the residue was dissolved in EtOAc (25 ml)and water (25 mL). The separated organic phase was dried over MgSO₄ andconcentrated in vacuo. The residue was purified by flash chromatographyon silica gel (solvent 3% EtOAc/hexane) to afford the title compound asa colourless solid (260 mg, 63% containing a 2:1 mixture ofdiastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.42-7.31 (m, 0.67H), 7.26-6.98 (m, 3H),6.94-6.78 (m, 2H), 6.69 (apr t, J=8.7 Hz, 1.33H), 4.08-3.83 (m, 4H),3.33 (dd, J=16.2 and 4.2 Hz, 0.67H), 3.03 (m, 0.67H), 2.78 (dd, J=15.9and 9.6 Hz, 0.33H), 2.53 (dd, J=15.9 and 5.4 Hz, 0.33H), 2.40 (d, J=2.1Hz, 0.67H), 2.10 (d, J=2.1 Hz, 0.33H), 1.11 (t, J=7.2 Hz, 2H), 1.07 (t,J=7.2 Hz, 1H).

EI-MS 346.2 [M⁺].

Methyl 3-(2,6-difluorophenyl)-4-(4-fluorophenyl)hex-5-ynoate 38

A solution of ethyl3-(2,6-difluorophenyl)-4-(4-fluorophenyl)-6-trimethylsilyl-hex-5-ynoate36 (100 mg, 0.24 mmol) and potassium carbonate (33 mg, 0.24 mmol) inmethanol (2 mL) was stirred at room temperature for 4 hours. The mixturewas concentrated in vacuo and the residue was purified by flashchromatography on silica gel (solvent 3% EtOAc/hexane) to afford thetitle compound as a colourless solid (30 mg, 40% containing a 5:3mixture of diastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.42-7.31 (m, 0.75H), 7.26-6.98 (m, 3H),6.94-6.78 (m, 2H), 6.71 (t, J=8.4 Hz, 1.25H), 4.11-3.88 (m, 2H), 3.59(s, 1.88H), 3.49 (s, 1.12H), 3.35 (dd, J=15.6 and 3.6 Hz, 0.63H), 3.06(dd, J=15.6 and 9.6 Hz, 0.63H), 2.81 (dd, J=15.9 and 9.0 Hz, 0.37H),2.60 (dd, J=15.9 and 5.1 Hz, 0.37H), 2.40 (d, J=2.1 Hz, 0.63H), 2.11 (d,J=2.4 Hz, 0.37H). EI-MS 332.2 [M⁺].

3-(2,6-difluorophenyl)-4-(4-fluorophenyl)hex-5-ynoic acid 39

A solution of ethyl3-(2,6-difluorophenyl)-4-(4-fluorophenyl)hex-5-ynoate 37 (160 mg, 0.48mmol) and lithium hydroxide (13 mg, 0.53 mmol) in tetrahydrofuran (3 mL)and water (0.3 mL) was stirred at 45° C. for 8 hours. A further portionof lithium hydroxide (13 mg, 0.53 mmol) was added to the mixture and themixture was then heated to 45° C. for 40 hours. Water (20 mL) anddichloromethane (10 mL) were added to the mixture and the separatedaqueous phase was washed with dichloromethane (3×10 mL). The pH of theaqueous phase was adjusted to pH 1 by dropwise addition of 2M aqueoushydrochloric acid and was extracted with dichloromethane (3×15 mL)before the combined organic fractions were dried over MgSO₄ andconcentrated in vacuo to afford the title compound as a colourless oilwhich solidified on standing (125 mg, 82% containing a 2:1 ratio ofdiastereoisomers).

¹H NMR (300 MHz, CDCl₃): 7.40-7.29 (m, 0.67H), 7.26-6.95 (m, 3H),6.95-6.75 (m, 2H), 6.69 (t, J=8.7 Hz, 1.33H), 4.06-3.81 (m, 2H), 3.36(dd, J=16.8 and 3.9 Hz, 0.67H), 3.07 (dd, J=16.8 and 10.5 Hz, 0.67H),2.82 (dd, J=16.8 and 9.3 Hz, 0.33H), 2.62 (dd, J=16.8 and 5.4 Hz,0.33H), 2.38 (d, J=2.1 Hz, 0.67H), 2.11 (d, J=2.4 Hz, 0.33H).

ESI-MS 319.1 [M+H⁺].

Example 3 2-Bromo-1-(2-chloro-4-(methylsulfonyl)phenyl)ethanone 41

1-(2-Chloro-4(methylsulfonyl)phenyl)ethanone was prepared according tothe procedure provided in Zuo et al. Shijie Nongyao (2007), 29(6),15-21. A solution of bromine (0.2 mL, 3.92 mmol) in chloroform (5 mL)was added dropwise to a suspension of1-(2-chloro-4(methylsulfonyl)phenyl)ethanone (960 mg, 4.13 mmol) andaluminium chloride (10 mg, 0.08 mmol) in chloroform (10 mL) at −5° C.The mixture was warmed to ambient temperature and stirred for 20 hours,after which time the reaction was quenched by addition of water (5 mL).The aqueous layer was extracted with chloroform (3×15 mL) before thecombined organics were washed with brine (20 mL), dried over MgSO₄ andthe solvent removed in vacuo. The crude material was purified by flashchromatography on silica gel (solvent 50% EtOAc/hexane) to afford thetitle compound as a white solid (1.03 g, 80%).

¹H NMR δ_(H) (CDCl₃, 300 MHz): 8.08 (s, 1H), 7.97 (d, J=6.0 Hz, 1H),7.74 (d, J=6.0 Hz, 1H), 4.49 (s, 2H), 3.13 (s, 3H) ppm. ESI-MS 312.9[MH]⁺.

5-(2-Chloro-4-methylsulfonylphenyl)-3H-imidazol[2,1][1,2,4]triazole 42

3-Amino-1,2,4-triazole (311 mg, 3.71 mmol) was dissolved in toluene (5mL) and heated to 110° C. A solution of2-bromo-1-(2-chloro-4-(methylsulfonyl)phenyl ethanone 41 (550 mg, 1.85mmol) in toluene (10 mL) (with the minimum amount of DMF needed for fulldissolution) was added portion wise to the solution over 3 hours. Thereaction was maintained at this temperature for 16 hours after whichtime TLC showed complete consumption of the starting material. Thevolatiles were removed in vacuo before the crude material was purifiedby flash chromatography on silica gel (solvent EtOAc) to afford thetitle compound as a yellow solid (90 mg, 8%).

¹H NMR δ_(H) (DMSO-d6, 300 MHz): 8.51 (s, 1H), 8.31 (d, J=9.0 Hz, 1H),8.05 (s, 1H), 7.93 (s, 1H), 7.84 (d, J=9.0 Hz, 1H), 3.21 (s, 3H) ppm.ESI-MS 297.0 [MH]⁺.

5-(2-Chloro-4-methylsulfonylphenyl)-1-methyl-6H-pyrazolo[3,4-d]imidazole43

Phosphorus(V) oxychloride (21.18 mL, 22.72 mmol) was added to a mixtureof 1-methyl-1H-4,5-diamine (844 mg, 5.68 mmol) and2-chloro-4-(methylsulfonyl)benzoic acid (1.33 g, 5.68 mmol) and themixture heated at 100° C. for 20 hours after which time TLC showedcomplete consumption of the starting material. The reaction was allowedto cool before being poured onto ice (˜100 g). DCM (50 mL) was addedbefore the mixture was made alkaline using 50% NaOH_((aq)). Aprecipitate formed which was removed by filtration. The organic layerwas separated and the aqueous layer was extracted with DCM (2×50 mL)before the organics were combined, washed with brine (2×50 mL), driedover MgSO₄ and the solvent removed in vacuo. The crude material waspurified by flash chromatography on silica gel (solvent 2% MeOH/EtOAc)to afford the title compound as a yellow solid (193 mg, 11%).

¹H NMR δ_(H) (DMSO-d6, 300 MHz): 12.49 (br, 1H), 8.15-8.02 (m, 2H),8.02-7.99 (m, 1H), 7.45 (s, 1H), 3.91 (s, 3H). (1 signal (3H) is missingbeneath the residual solvent peak). ESI-MS 311.0 [MH]⁺.

Example 4 2-Methyl-3-methylsulfanyl-4-(trifluoromethyl)benzaldehyde 45

2-Methyl-3-methylsulfanyl-4-(trifluoromethyl)benzoic acid was preparedaccording to the procedure provided in WO 2008125214. Borane-THF complex(2.6 mL, 1M in tetrahydrofuran, 2.60 mmol) was added to a solution of2-methyl-3-methylsulfanyl-4-(trifluoromethyl)benzoic acid (260 mg, 1.04mmol) in tetrahydrofuran (3 mL) and the mixture was stirred at roomtemperature for 17 h. Methanol (1 mL) was added, followed by water (10mL) and ethyl acetate (15 mL) and the mixture was extracted with ethylacetate (2×15 mL). The combined organic phases were dried over MgSO₄ andthe solvent removed in vacuo. Dess-Martin periodinane (453 mg, 1.07mmol) was added to a solution of this crude product (240 mg, 1.02 mmol)in dichloromethane (8 mL) and the mixture was stirred at roomtemperature for 1.5 h. Saturated aqueous sodium bicarbonate solution (10mL) was added and the mixture was extracted with dichloromethane (3×15mL). The combined organic phases were dried over MgSO₄ and concentratedto give the crude product which was purified by flash chromatography onsilica gel (solvent 10% EtOAc/hexane) to afford the title compound as acolourless oil (192 mg, 81%).

¹H NMR δ_(H) (300 MHz, CDCl₃); 10.34 (s, 1H), 7.81 (d, J=8.0 Hz, 1H),7.69 (d, J=8.0 Hz, 1H), 2.94 (s, 3H), 2.22 (s, 3H); EI-MS 234.0 [M⁺].

1-[2-Methyl-3-methylsulfanyl-4-(trifluoromethyl)phenyl]-N-(4-methyl-1,2,5-oxadiazol-3-yl)methanimine46

A solution of 2-methyl-3-methylsulfanyl-4-(trifluoromethyl)benzaldehyde45 (184 mg, 0.788 mmol) and 4-methyl-1,2,5-oxadiazol-3-amine (78 mg,0.788 mmol) in toluene (3 mL) was heated at 110° C. over 4 Å molecularsieves and MgSO₄ for 96 h after which time the mixture was filtered andconcentrated to give the title compound as a colourless solid (176 mg,71%).

¹H NMR δ_(H) (300 MHz, CDCl₃); 9.31 (s, 1H), 8.16 (d, J=8.0 Hz, 1H),7.63 (d, J=8.0 Hz, 1H), 2.88 (s, 3H), 2.37 (s, 3H), 2.22 (s, 3H); EI-MS315 [M⁺].

4-Methyl-N-[[2-methyl-3-methylsulfanyl-4-(trifluoromethyl)phenyl]methyl]-1,2,5-oxadiazol-3-amine47

Sodium borohydride (30 mg, 0.793 mmol) was added to a solution of1-[2-methyl-3-methylsulfanyl-4-(trifluoromethyl)phenyl]-N-(4-methyl-1,2,5-oxadiazol-3-yl)methanimine46 (100 mg, 0.317 mmol) in methanol (3 mL) and the mixture was stirredat room temperature for 1.5 h. Water (10 mL) and ethyl acetate (10 mL)were added and the aqueous layer was further extracted with ethylacetate (2×15 mL). The combined organic phases were dried (MgSO₄),filtered and concentrated to give the crude product which was purifiedby flash chromatography on silica gel (solvent 20% EtOAc/hexane) toafford the title compound as a colourless oil (77 mg, 76%).

¹H NMR δ_(H) (300 MHz, CDCl₃); 7.61 (d, J=9.0 Hz, 1H), 7.44 (d, J=9.0Hz, 1H), 4.59 (d, J=6 Hz, 2H), 3.92 (br s, 1H), 2.72 (s, 3H), 2.30 (s,6H); ESI-MS 318.0 [MH⁺].

2-Methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-methylsulfanyl-4-(trifluoromethyl)benzamide48

Oxalyl chloride (120 μL, 1.20 mmol) was added to a solution of2-methyl-3-methylsulfanyl-4-(trifluoromethyl)benzoic acid (200 mg, 0.80mmol) and N,N-dimethylformamide (2 drops) in dichloromethane (3.5 mL)and the mixture was stirred at room temperature for 2 h.

Concentration under reduced pressure gave the crude acid chloride (0.80mmol), which was used without further purification.

Sodium bis(trimethylsilyl)amide (1M solution in tetrahydrofuran, 1.2 mL,1.20 mmol) was added to a solution of 4-methyl-1,2,5-oxadiazol-3-amine(95 mg, 96 mmol) in tetrahydrofuran (2 mL) at −78° C. and the mixturewas stirred at that temperature for 1 h. The mixture was graduallyallowed to warm to −30° C. and a solution of the acid chloride (0.8mmol) in tetrahydrofuran (2 mL) was added. The mixture was allowed towarm to room temperature and was stirred for 16 h. Saturated ammoniumchloride solution (10 mL) and ethyl acetate (10 mL) were added, theorganic layer separated and the aqueous layer further extracted withethyl acetate (2×15 mL). The combined organic phases were dried (MgSO₄),filtered and concentrated to give the crude product which was purifiedby flash chromatography on silica gel (solvent 33% Et₂O/hexane) toafford the title compound as a colourless oil (84 mg, 32%).

¹H NMR δ_(H) (300 MHz, CDCl₃); 7.78 (br s, 1H), 7.56 (d, J=8.0 Hz, 1H),7.44 (d, J=8.0 Hz, 1H), 2.65 (s, 3H), 2.35 (s, 3H), 2.16 (s, 3H); ESI-MS354.0 [MNa⁺].

Compound 48 forms part of the prior art (WO2011/035874) and is includedfor reference purposes only.

Example 6 Testing the Herbicidal Activity of Compounds of the Invention

Compounds 22, 23 and 24 were screened for herbicidal efficacy againsttarget plants: garden cress, Lepidium sativum, common chickweed,Stellaria media, and white mustard Sinapsis alba

Test Systems

Plants were obtained as seeds and were grown to the 2-4 true leaf stage.Plants were grown under laboratory conditions, individually in seedtrays. Each plant (in an approximately 3 cm diameter plug) was thendetached from the tray for spraying.

Environmental conditions were closely monitored and recorded and werewithin the optimal range of the target species.

Test Treatments and Application

The compounds were screened at a range of five concentrations, dilutedin acetone and Tween™. A carrier only control was also conducted.Treatments were applied directly onto the plants, using a potter tower,at a specified application rate.

Experimental Design

One plant of each species was sprayed using a potter tower. The 3different types of plants were placed on a 10 cm diameter platformdirectly beneath the potter sprayer and sprayed simultaneously. Thegrowth of the plants and any Phytotoxicity effects were then assessed atintervals over 21 days, according to EPPO guideline PP1/135.

Five replicas were performed for each treatment, for each species.

In the tables below C represents a percentage increase in necrosisrelative to the control of 0.1-50; B represents a percentage inhibitionof 50-80; and A represents a percentage inhibition of 80-100.

TABLE 1A Chickweed Average of necrosis Dose Days post applicationCompound g/ha 1 2 3 4 5 7 10 14 22 200 C C C B A A A 100 C C C B A A A50 C C C B B B A 25 C C C C A A A 12.5 C C C C B B B 23 200 C C C C B BB 100 C C C C B B A 50 C C C C B B B 25 C C C C B B B 12.5 C C C C B B A24 200 C C C C A A A 100 C C C B B B A 50 C C C C A A A 25 C C C C C C C12.5 C C C C C C C untreated 0 C C C C C C C C

TABLE 1B Garden Cress Average of necrosis Dose Days post applicationCompound g/ha 1 2 3 4 5 7 10 14 22 200 C C C C B B A 100 C C C C B B B50 C C C C B B B 25 C C C C C C A 12.5 C C C C C C B 23 200 C B B B B BB 100 C C C C B B B 50 C C C C B B B 25 C C C C C C B 12.5 C C C C C C C24 200 C C C C C C B 100 C C C B B B B 50 C C B B B A A 25 C C C C C C C12.5 C C C C C C B untreated 0 C C C C C C C C

TABLE 1C Mustard Average of necrosis Dose Days post application Compoundg/ha 1 2 3 4 5 7 10 14 22 200 C C C C C C B 100 C C C C C C B 50 C C C CB B B 25 C C C C C C C 12.5 C C C C C C B 23 200 C C C C C C C 100 C C CC C C C 50 C C C C C C C 25 C C C C C C C 12.5 C C C C C C C 24 200 C CC C C C C 100 C C C C C C C 50 C C C C C C C 25 C C C C C C C 12.5 C C CC C C C untreated 0 C C C C C C C C

Certain compounds of the invention were screened for herbicidal efficacyagainst target plants: Amaranthus retroflexus (redroot pigweed),Abutilon theophrasti (China Jute): Capsella bursa-pastoris,(shepherd's-purse) Echinochloa crus-galli, Hordeum vulgare (Barley),

TABLE 2 Average of corrected necrosis Compound 25 22 24 26 Days postapplication 1 7 1 7 1 7 1 7 A. retroflexus 6.25 g/ha C A C A C A C A12.5 C A C A C A C A 25 C A C A C A C A 50 C A C A C A C A 100 C A C A CA C A A. theophrasti 6.25 C A C A 0 A C A 12.5 C A C A 0 A 0 A 25 C A CA 0 A C A 50 C A C A 0 A C A 100 C A C A C A B A C. bursa pastoris 6.250 A 0 A C A C A 12.5 0 A C A 0 B C 0 25 0 A C A C A C A 50 C A 0 A C A CA 100 C A C A C A C A

All compounds for which the data is presented in table 2 showedexcellent control over all target weed species after 7 days. Indeed,compound 26 showed better control than the reference compound(saflufenacil), against certain weed species after 1 day indicating thatit is faster acting.

TABLE 3 Average of % corrected necrosis Compound 34 27 37 27a 30 Daysafter application 1 4 10 16 1 4 10 16 4 7 10 4 7 10 4 7 10 A.theophrasti 10 0 C C C 0 C C C 20 0 C C C 0 C 0 0 C C C C B B C C B 40 CC C C C C 0 0 C B B C C C C C C 80 C C C C C C 0 0 B A A C B B 0 C C 160C C C C C C C 0 C C C C B B C B B E. crus galli 10 C C C C 0 0 C C 20 CC C C 0 C 0 0 C C C C C C 0 C 0 40 C C C C 0 0 0 0 B B B B B B 0 C C 800 C C C 0 0 0 C A A A C C C 0 0 0 160 0 C C C C C C C B B A C C C C C CH. vulgare 10 0 C C C 0 0 C C 20 0 C C C 0 0 0 0 C C C C C C C C C 40 0C C C 0 C 0 0 C C C C C C 0 0 C 80 0 C C C 0 0 0 0 C A A C C C 0 0 C 1600 C C C 0 C C C C C B 0 B B C C C Compound 28 35 29 39 38 Days afterapplication 4 7 10 4 7 10 4 7 10 4 7 10 4 7 10 A. theophrasti 10 20 C CC C C C 0 C A C C C C B B 40 C B B C C C C C B C C B C C C 80 C C C C CC C C B C C B C C B 160 C C B C C C C C B C B A C C B E. crus galli 1020 C C C 0 C C 0 C C 0 C C 0 0 0 40 B C C 0 0 0 C C C 0 B B C B B 80 0 CC 0 0 0 C C C 0 0 0 C B B 160 C C C 0 C C C C B C C C C C C H. vulgare10 20 0 C C 0 C C 0 B B 0 0 0 0 0 0 40 0 C C 0 0 0 0 C C 0 0 C 0 C C 800 0 0 0 0 0 0 C C 0 0 0 0 C C 160 0 C C 0 0 0 0 C C 0 C C 0 C C

All compounds for which the data is presented in table 3 showed activityagainst all target weed species.

In particular, compound 37 showed excellent control over all three weedspecies. Indeed, compound 37 showed significantly better control thanprior art compounds with known activity (compound 27 and 27a)

TABLE 4 Average of % corrected necrosis Compound 49 42 43 Days afterapplication 1 4 10 16 1 4 10 16 1 4 10 16 A. theophrasti 10 C C C C C C0 0 C C B B 20 C C C C C C C C C C C C 40 C 0 C C 0 0 C C C C C C 80 C 0C C 0 C C C C C 0 0 160 0 C 0 C 0 C C C C C 0 0 E. crus galli 10 0 C C CC C 0 C 0 0 C C 20 0 0 0 0 0 C C C C C 0 0 40 C 0 C C C C C C 0 C 0 0 800 0 C C C C C C C C 0 0 160 0 C 0 0 0 C C C 0 C 0 0 H. vulgare 10 0 0 CC 0 0 0 0 0 C C C 20 0 0 C C 0 0 0 C 0 0 0 0 40 0 0 C C 0 C C C 0 0 0 080 0 0 C C 0 C C C 0 C 0 0 160 0 0 0 0 0 0 C C 0 C 0 0

All compounds for which the data is presented in table 4 showed activityagainst all target weed species.

Compound 49 forms part of the prior art (WO2013/017559) and is includedas a reference only:

TABLE 5 Average of % corrected necrosis Compound 47 46 48 Days afterapplication 4 7 10 4 7 10 4 7 10 A. theophrasti 6.25 C C C C C B 12.5 CC A C C C C C B 25 C C B C C B C C B 50 C C B C C B C C B 100 C B B B BB C B B E. crus galli 6.25 C C C C C C 12.5 C C B C C C C C C 25 C C B 00 C C C C 50 C C B C C C C C C 100 C C B B B A C B B H. vulgare 6.25 0 00 0 C C 12.5 C C C 0 0 0 C C C 25 C C B 0 C C C C C 50 C C B C C C 0 C C100 C C B C C C 0 C A

All compounds for which the data is presented in Table 5 showed activityagainst all tested weed species. Both compound 47 and 48 showed goodcontrol over A. theophrasti and E. crus galli after 10 days, withcompound 47 also showing good control over H. vulgare. Indeed, compound47 showed improved control of E. crus galli and H. vulgare at lowdosages relative to the reference compound 48, a compound with knownactivity.

1. A compound of formula

wherein

represents a single bond or a double bond; X is independently NR⁶ orCR⁷R⁷;

X¹ is selected from: ═O, —R⁷ or (—R⁷)₂; with the proviso that if

X¹ is ═O, X is CR⁷R⁷; R¹ and R³ are each independently at eachoccurrence selected from C₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen, nitro,OR⁸, SR⁸, cyano, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl andNR⁸R⁸; R² and R⁶ are each independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl; R⁴ is absent or is independentlyselected from: H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl; R⁵is independently selected from C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄haloalkyl; R⁷ is independently at each occurrence selected from: H,C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl; R⁸ is independentlyat each occurrence selected from; H, C₁-C₄ alkyl, C(O)—C₁-C₄-alkyl andC₁-C₄ haloalkyl; n is an integer selected from 0, 1 and 2; p is aninteger independently selected from 0, 1, 2 and 3; wherein in any R¹-R⁸group which contains an alkyl, haloalkyl, cycloalkyl, heterocycloalkyl,aryl (including phenyl, biphenyl and naphthyl) or heteroaryl group, thatalkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl groupis optionally substituted, where chemically possible, by 1 to 4substituents which are each independently selected at each occurrencefrom the group consisting of: oxo; ═NR^(a); ═NOR^(a); R^(a); halo;nitro; cyano; NR^(a)R^(a); SO₃R^(a); SO₃R^(a); SO₂NR^(a)R^(a);C₂O₂R^(a); C(O)R^(a); CONR^(a)R^(a); CH₂NR^(a)R^(a); CH₂OR^(a) andOR^(a); wherein R^(a) is selected from H, C₁-C₄ alkyl and C₁-C₄haloalkyl; and wherein, in the case of an aryl group or heteroarylgroup, any two of these substituents (e.g. NR^(a)R^(a), OR^(a), SR^(a),R^(a)) when present on neighbouring atoms in the aryl or heteroarylgroup may, where chemically possible, together with the atoms to whichthey are attached form a ring which is fused to the aryl or heteroarylgroup; or an agronomically acceptable salt or N-oxide thereof.
 2. Thecompound of claim 1, wherein, the compound is a compound of formula II:


3. The compound of claim 1, wherein the compound is a compound offormula III:

wherein R⁴ is independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.
 4. The compound of claim 1,wherein the compound is a compound of formula IV:


5. The compound of claim 1, wherein the compound is a compound offormula V:


6. The compound of claim 1, wherein the compound is a compound offormula VI:

wherein R⁴ is independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.
 7. The compound of claim 1,wherein the compound is a compound of formula VII:

wherein R⁴ is independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.
 8. The compound of claim 1,wherein the compound is a compound of formula XXIX:

and wherein R⁴ is independently selected from: H, C₁-C₄ alkyl,C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.
 9. The compound of claim 1,wherein X is CR⁷R⁷.
 10. The compound of claim 1, wherein n is 1,optionally wherein R¹ is selected from C₁-C₄ alkyl, C₁-C₄-haloalkyl,halogen and C₃-C₆ cycloalkyl.
 11. The compound of claim 1, wherein R³ isindependently selected from: C₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen andC₃-C₆ cycloalkyl.
 12. The compound of claim 1, wherein R² is selectedfrom: C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl.
 13. Thecompound of claim 1, wherein R⁴ is H.
 14. The compound of claim 1,wherein R⁵ is C₁-C₄ alkyl.
 15. A compound of formula VIII:

wherein Y is independently selected from O, NR¹³ and CR¹⁴R¹⁴; R⁹ and R¹²are each independently at each occurrence selected from C₁-C₄ alkyl,C₁-C₄-haloalkyl, halogen, nitro, OR¹⁵, SR¹⁵, cyano, C₂-C₄ alkenyl, C₂-C₄alkynyl, C₃-C₆ cycloalkyl and NR¹⁵R¹⁵; R^(10a) is independently selectedfrom CN and —C≡C—R^(10c); R^(10b) is independently selected from: H,C₁-C₄ alkyl and C₁-C₄ haloalkyl; R^(10c) is independently selected fromH and C₁-C₂-alkyl; R¹¹ is selected from H, OR^(16a), C(O)R^(16a),CO₂—R^(16b), CH²—O—R^(16b), S(O)OR^(16b), SO₃R^(16b) andP(O)(OR^(16b))₂; with the proviso that if Y is CR¹⁴R¹⁴ and R¹⁰ is CN,R¹¹ is not CO₂R^(16b); R¹³, R¹⁴ and R^(16b) are each independently ateach occurrence selected from: H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl andC₁-C₄ haloalkyl; R^(16a) is independently selected from: unsubstitutedC₁-C₄ alkyl, C₃-C₆-cycloalkyl and unsubstituted haloalkyl; R¹⁵ isindependently at each occurrence selected from; H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl; q and r are each independently aninteger selected from 0, 1, 2, 3, 4 and 5; wherein in any R⁹-R¹⁵,R^(16a) or R^(16b) group which contains an alkyl, haloalkyl, cycloalkyl,heterocycloalkyl, aryl (including phenyl, biphenyl and naphthyl) orheteroaryl group, that alkyl, haloalkyl, cycloalkyl, heterocycloalkyl,aryl or heteroaryl group is optionally substituted, where chemicallypossible, by 1 to 4 substituents which are each independently selectedat each occurrence from the group consisting of: oxo; ═NR^(a); ═NOR^(a);R^(a); halo; nitro; cyano; NR^(a)R^(a); SO₃R^(a); SO₂R^(a);SO₂NR^(a)R^(a), CO₂R^(a), C(O)R^(a); CONR^(a)R^(a); CH₂NR^(a)R^(a);CH₂OR^(a) and OR^(a); wherein R^(a) is selected from H, C₁-C₄ alkyl andC₁-C₄ haloalkyl; and wherein, in the case of an aryl group or heteroarylgroup, any two of these substituents (e.g. NR^(a)R^(a), OR^(a), SR^(a),R^(a)) when present on neighbouring atoms in the aryl or heteroarylgroup may, where chemically possible, together with the atoms to whichthey are attached form a ring which is fused to the aryl or heteroarylgroup; or an agronomically acceptable salt or N-oxide thereof, with theproviso that the compound is not


16. A compound of formula XVIII:

wherein A is independently selected from a furazan, a tetrazole and a1,2,4-triazole; L is independently selected from: —NR¹⁹—CH₂—, —O—N—CH—,—N═CH— and —NR¹⁹SO₂—; R¹⁸ is independently at each occurrence selectedfrom C₁-C₄ alkyl, C₁-C₄-haloalkyl, halogen, nitro, OR²⁰, SR²⁰, SO₂R²⁰,cyano, C₂-C₄ alkenyl, C₃-C₆ cycloalkyl and NR²⁰R²⁰; R¹⁹ is independentlyselected from H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄ haloalkyl; R²⁰is independently at each occurrence selected from H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl; s is an integer independentlyselected from 0, 1, 2, 3, 4 and 5; wherein in any R¹⁷-R²⁰ group whichcontains an alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl(including phenyl, biphenyl and naphthyl) or heteroaryl group, thatalkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl groupis optionally substituted, where chemically possible, by 1 to 4substituents Which are each independently selected at each occurrencefrom the group consisting of oxo; ═NR^(a); ═NOR^(a); R^(a); halo; nitro;cyano; NR^(a)R^(a); SO₃R^(a); SO₂R^(a); SO₂NR^(a)R^(a); CO₂R^(a);C(O)R^(a); CONR^(a)R^(a); CH₂NR^(a)R^(a); CH₂OR^(a) and OR^(a); whereinR^(a) is selected from H, C₁-C₄ alkyl and C₁-C₄ haloalkyl; and wherein,in the case of an aryl group or heteroaryl group, any two of thesesubstituents (e.g. NR^(a)R^(a), OR^(a), SR^(a), R^(a)) when present onneighbouring atoms in the aryl or heteroaryl group may, Where chemicallypossible, together with the atoms to which they are attached form a ringwhich is fused to the aryl or heteroaryl group; or an agronomicallyacceptable salt or N-oxide thereof.
 17. A compound of formula XXI:

wherein R²² is independently selected from

Z¹ and Z² are each independently selected from N and CR¹⁷; R¹⁷ and R¹⁸are each independently at each occurrence selected from C₁-C₄ alkyl,C₁-C₄-haloalkyl, halogen, nitro, OR²⁰, SR²⁰, SO₂R²⁰, cyano, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl and NR²⁰R²⁰; R²⁰ isindependently at each occurrence selected from H, C₁-C₄ alkyl,C(O)—C₁-C₄-alkyl and C₁-C₄ haloalkyl; R²¹ is independently at eachoccurrence selected from H, C₁-C₄ alkyl, C₃-C₆-cycloalkyl and C₁-C₄haloalkyl; s is an integer independently selected from 0, 1, 2, 3, 4 and5; wherein in any R¹⁷-R²¹ group which contains an alkyl, haloalkyl,cycloalkyl, heterocycloalkyl, aryl (including phenyl, biphenyl andnaphthyl) or heteroaryl group, that alkyl, haloalkyl, cycloalkyl,heterocycloalkyl, aryl or heteroaryl group is optionally substituted,where chemically possible, by 1 to 4 substituents which are eachindependently selected at each occurrence from the group consisting of:oxo; ═NR^(a); —NOR^(a); R^(a); halo; nitro; cyano; NR^(a)R^(a);SO₃R^(a); SO₂R^(a); SO₂NR^(a)R^(a); CO₂R^(a), C(O)R^(a); CONR^(a)R^(a);CH₂NR^(a)R^(a); CH₂OR² and OR^(a); wherein R^(a) is selected from H,C₁-C₄ alkyl and C₁-C₄ haloalkyl; and wherein, in the case of an arylgroup or heteroaryl group, any two of these substituents (e.g.NR^(a)R^(a), OR^(a), SR^(a), R^(a)) when present on neighbouring atomsin the aryl or heteroaryl group may, where chemically possible, togetherwith the atoms to which they are attached form a ring which is fused tothe aryl or heteroaryl group; or an agronomically acceptable salt orN-oxide thereof.
 18. A method for controlling the weeds, the methodcomprising applying an agronomically effective and substantiallynon-phytotoxic (to the crop plant) quantity of a compound of claim 1 tothe plants themselves or to the area where it is intended that theplants will grow.
 19. A herbicidal composition comprising an effectiveamount of an active compound of claim
 1. 20. The compound of claim 1,wherein X is NR⁶.